Low emissions, high working capacity adsorbent and canister system

ABSTRACT

The present description provides high working capacity adsorbents with low DBL bleed emission performance properties that allows the design of evaporative fuel emission control systems that are lower cost, simpler and more compact than those possible by prior art. Emission control canister systems comprising the adsorbent material demonstrate a relatively high gasoline working capacity, and low emissions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority to U.S. ProvisionalPatent Application Ser. No. 62/565,699 titled: LOW EMISSIONS, HIGHWORKING CAPACITY ADSORBENT AND CANISTER SYSTEM, filed Sep. 29, 2017, andU.S. patent application Ser. No. 16/149,045 titled: LOW EMISSIONS, HIGHWORKING CAPACITY ADSORBENT AND CANISTER SYSTEM, filed Oct. 1, 2018;which are hereby incorporated by reference in their entirety for allpurposes.

BACKGROUND 1. Field of the Discovery

The present disclosure, in various embodiments, relates generally toevaporative emission control systems.

2. Background Information

Evaporation of gasoline fuel from motor vehicle fuel systems is a majorpotential source of hydrocarbon air pollution. These fuel vaporemissions occur when the vehicle is running, refueling, or parked—engineoff. Such emissions can be controlled by the canister systems thatemploy activated carbon to adsorb the fuel vapor emitted from the fuelsystems. Under certain modes of engine operation, the adsorbed fuelvapor is periodically removed from the activated carbon by purging thecanister systems with ambient air to desorb the fuel vapor from theactivated carbon. The regenerated carbon is then ready to adsorbadditional fuel vapor.

It is well known in the art that a more space efficient activated carbonadsorbent for this application is characterized by an n-butane vaporadsorption isotherm that has adsorption capacity steeply sloped towardshigh vapor partial pressures (U.S. Pat. No. 6,540,815). In that way, theadsorbent has a high capacity at relatively high concentrations of thetype of vapors present with gasoline fuel, and the adsorbent favorsrelease of these captured vapors when exposed to a low vaporconcentration or partial pressure, such as during purge. These highperformance activated carbons have a large amount of pore volume as“small mesopores” (e.g., SAE Technical Papers 902119 and 2001-03-0733,and Burchell 1999, pp. 252-253), which are preferably about 1.8 nm toabout 5 nm in size as measured by the BJH method of analysis of nitrogenadsorption isotherms (e.g., U.S. Pat. No. 5,204,310). (According toIUPAC classification, these are pores of about 1.8-2 nm size within the<2 nm micropore size range, plus pores of about 2-5 nm size within the2-50 nm mesopore size range). The small mesopores are sufficiently smallto capture vapors as a condensed phase, and yet readily empty uponexposure to a low partial pressure of vapor. Accordingly, the volume inthese pores correlates linearly with the recoverable vapor capacity bythe adsorbent in a canister volume, known as gasoline working capacity(GWC), and likewise correlates linearly with the ASTM butane workingcapacity (BWC) of the adsorbent, as measured by the standard ASTM 5228method, which are incorporated herein by reference. Generally, the rangeof ASTM BWC of commercial activated carbon products for this applicationis from about 3 to about 17 g/dL, with 9+ g/dL BWC carbons favored forworking capacity towards the fuel vapor source of the canister system,and lower BWC carbons used in one or more subsequent volumes towards theatmosphere port or vent-side (i.e., vent-side adsorbent volumes).Generally, cylindrical pellet and other engineered shaped (e.g.,spherical granule) activated carbons are preferred over irregularlyshaped or crushed particulates, especially for canister systems wheremoderated flow restriction is required such as for vapor capture duringrefueling. Advantages of pelletized and engineered shaped activatedcarbons include good mechanical strength, low dust, low dusting rate,high on-size yield in processing, and a narrow particle sizedistribution that provides consistency across liter-size canister fillsafter bulk shipment and handling.

Several approaches have been described for preparing pelletized andengineered shaped activated carbons. One group of approaches involvesbinding carbon powder that is already activated (“grind & bind”). Forexample, U.S. Pat. No. 4,677,086 describes the use of a bentonite claybinder, U.S. 20060154815A1 describes acrylic or acryl-styrene emulsionwith CMC binder system, U.S. Pat. No. 6,277,179 describes thermosettingresin binders, and U.S. Pat. No. 6,472,343 describes crosslinked binder,such as carboxymethyl cellulose (CMC). Advantages of grind & bindinclude control of mechanical strength and dusting properties inpost-activation processing, independent of the pore-forming activationprocess. However, the nonadsorptive binders are a diluent, and the grind& bind processing can damage the adsorbent carbon porosity. See U.S.Pat. No. 6,277,179 and its references for the problem of loss inadsorptive properties due to pore blocking and contamination frombinders. Furthermore, inert atmospheres are needed with certain bindersthat require heat treatments in order to avoid combustion of theactivated carbon ingredient, and, regardless, collapse of adsorptiveporosity can occur, especially for activated carbon ingredients notpreviously exposed to such elevated temperatures during activationprocessing. Nevertheless, the grind & bind approach is useful forproviding moderate levels of BWC in pelletized activated carbons (e.g.,about 9.5 to 12 g/dL BWC). Example commercial products favored forworking capacity towards the fuel vapor source are clay-bound NUCHAR®BAX 950, BAX 1000, and BAX 1100 and organic-bound NUCHAR® BAX 1100LD(Ingevity Corporation, North Charleston, S.C.), which all have BWCproperties below 12.3 g/dL.

The grind & bind approach is also useful in forming specially shapedpellets (e.g., U.S. Pat. Nos. 9,174,195 and 9,322,368, with commercialexample of MPAC1 (Kuraray Chemical Ltd, Bizen-shi Japan), volumetricallydiluted pellets (U.S. RE38,844 with a commercial example of NUCHAR® BAXLBE), and high heat capacity pellets (U.S. Pat. No. 6,599,856). As aconsequence of the special shaping and non-adsorptive additives, the BWCof the pelletized activated carbon is diluted in each case to below 9.5g/dL and they are effective for suppressing diurnal bleed emissions whenthese special pellets are in vent-side volumes within the canistersystem.

Another group of approaches for preparing pelletized activated carboninvolves first shaping a carbonaceous precursor or char, and thenactivating for forming the adsorptive porosity (“shape & activate”).See, e.g., U.S. Pat. Nos. 5,039,651, 5,204,310, 5,250,491, 5,324,703, EP0 423 967B1, and CN102856081 for acid activation processes, and U.S.20080063592A1 for a thermal activation process. These methods areessentially “binderless” in that the component providing structuralintegrity and mechanical strength to the shaped material is a nativeconstituent of the carbonaceous precursor, or if a resin or pitch binderingredient is added (e.g., U.S. Pat. Nos. 3,864,277 and 5,538,932), thebinder ingredient is converted to activated carbon in the process, thusalso contributing to the adsorptive performance of the final product.U.S. Pat. No. 5,324,703 employs phosphoric acid activation with sawdustfor preparing activated carbon pellets with BWC properties as high as 17g/dL, by a process that minimizes macropore volume and thus maximizesthe volumetric content in the pellet of pores in the target 1.8-5 nmsize range that are known to be effective for gasoline vapor workingcapacity. These shape & activate methods are efficient means to providethe greatest volume of adsorptive pores per liter of canister fill,without non-adsorptive additives or fillers. The activated carbonsprepared by shape & activate processes are the shaped product itself, asthe process does not require subsequent grinding, metering of binder andpore-protecting ingredients, shaping, and further drying and heattreatments. Commercial examples of shape & activate include NUCHAR® BAX1500, BAX 1500E, BAX 1700 (Ingevity Corporation, N. Charleston, S.C.,USA); CNR 115, CNR 120, CNR 150 (Cabot Corporation, Boston, Mass., USA),3GX (Kuraray Chemical Ltd, Bizen-shi Japan), and KMAZ2 and KMAZ3 (FujianXinsen Carbon, Fujian Sheng, China). The BWC properties for these shape& activate products range from about 11 g/dL to about 17 g/dL. Shape &activate technology has been the accepted and only commercial technologyfor high working capacity carbon pellets for evaporative emissioncontrol (e.g., defined here as BWC above 13 g/dL), for the reasons ofeconomy of process steps, lower manufacturing costs, and effectivenessfor instilling the highest BWC properties. The advantages of the highworking capacity for canister systems include reducing the size andweight of the canister system by requiring less activated carbon volume,and by increasing the bed volumes of purge available (liters purge perliters of canister system) which is a key factor for system workingcapacity and emissions performance. See, e.g., SAE papers 2000-01-0895and 2001-01-0733.

Though a highly mesoporous adsorbent is favored for working capacity,high ASTM BWC of the adsorbent and its high GWC appear to run counter,in practice, from the concurrent need of the fuel vapor emission controlsystem to provide low emissions even when the vehicle is not operating.

For example, an increase in environmental concerns has continued todrive strict regulations of those hydrocarbon emissions. When a vehicleis parked in a warm environment during the daytime heating (i.e.,diurnal heating), the temperature in the fuel tank increases resultingin an increased vapor pressure in the fuel tank. Normally, to preventthe leaking of the fuel vapor from the vehicle into the atmosphere, thefuel tank is vented through a conduit to a canister containing suitablefuel adsorbent materials that can temporarily adsorb the fuel vapor. Thecanister defines a vapor or fluid stream path such that when the vehicleis at rest the fuel vapor of fluid passes from the fuel tank, throughthe fuel tank conduit, through one or more adsorbent volumes, and out toa vent port, which opens to the atmosphere. A mixture of fuel vapor andair from the fuel tank enters the canister through a fuel vapor inlet ofthe canister and diffuses into the adsorbent volume where the fuel vaporis adsorbed in temporary storage and the purified air is released to theatmosphere through a vent port of the canister. Once the engine isturned on, ambient air is drawn into the canister system through thevent port of the canister. The purge air flows through the adsorbentvolume inside the canister and desorbs the fuel vapor adsorbed on theadsorbent volume before entering the internal combustion engine througha fuel vapor purge conduit. The purge air does not desorb the entirefuel vapor adsorbed on the adsorbent volume, resulting in a residuehydrocarbon (“heel”) that may be emitted to the atmosphere.

In addition, the heel in local equilibrium with the gas phase alsopermits fuel vapors from the fuel tank to migrate through the canistersystem as emissions. Such emissions typically occur when a vehicle hasbeen parked and subjected to diurnal temperature changes over a periodof several days, commonly called “diurnal breathing loss” (DBL)emissions. The California Low Emission Vehicle Regulations make itdesirable for these DBL emissions from the canister system to be below10 mg (“PZEV”) for a number of vehicles beginning with the 2003 modelyear and below 50 mg, typically below 20 mg, (“LEV-II”) for a largernumber of vehicles beginning with the 2004 model year.

Now the California Low Emission Vehicle Regulation (LEV-III) and UnitedStates Federal Tier 3 regulations require canister DBL emissions not toexceed 20 mg as per the Bleed Emissions Test Procedure (BETP) as writtenin the California Evaporative Emissions Standards and Test Proceduresfor 2001 and Subsequent Model Motor Vehicles, Mar. 22, 2012.Furthermore, the regulations on DBL emissions continue to createchallenges for the evaporative emission control systems, especially whenthe level of purge air is low. For example, the potential for DBLemissions may be more severe for a hybrid vehicle, including a vehiclewhose powertrain is both an internal combustion engine and an electricmotor (“HEV”), and a vehicle where there is a start-stopsystem/stop-start system that automatically shuts down and restarts theinternal combustion engine to reduce the amount of time the enginespends idling, thereby reducing fuel consumption and tailpipe emissions.In such hybrid vehicles, the internal combustion engine is turned offnearly half of the time during vehicle operation. Since the adsorbedfuel vapor on the adsorbents is purged only when the internal combustionengine is on, the adsorbents in the canister of a hybrid vehicle ispurged with fresh air less than half of the time compared toconventional vehicles and frequently within the range of 55 BV to 100BV, where “BV” is the ratio of the total volume of purge flow relativeto the volumes of adsorbent in the canister system. And yet, hybridvehicles generate nearly the same amount of evaporative fuel vapor asconventional vehicles. The lower purge frequency and lower purge volumeof the hybrid vehicle can be insufficient to clean the residuehydrocarbon heel from the adsorbents in the canister, resulting in highDBL emissions. Other powertrains when engineered for optimum driveperformance, fuel efficiency and tailpipe emissions, are similarlychallenged to provide a high level of purge for refreshing the canisterand are challenged to provide optimum air-fuel mixtures and rates to theengine. These powertrains include turbocharged or turbo-assistedengines, and gasoline direct injection (“GDI”) engines.

Globally, by contrast, evaporative emission regulations have been lessstringent than in the US, but the trend is now for more stringentregulations, along the path that the US has taken. There is increasedrecognition of the benefits from tighter controls for better use ofvehicle fuel and for cleaner air, especially in regions where light dutyvehicle use is growing rapidly and air quality issues require urgentattention. As a notable example, the Ministry of EnvironmentalProtection of the People's Republic of China released regulations in2016 that include limitations on fuel vapor emissions, forimplementation in 2020 (See “Limits and Measurement Methods forEmissions from Light-Duty Vehicles, GB 18352.6-2016, also known as“China 6”). This standard specifies the limits and measurement methodsfor light-duty vehicles, including hybrid electric vehicles, equippedwith positive ignition engines for exhaust emissions in regular and lowtemperatures, real driving emissions (RDE), crankcase emissions,evaporative emissions and refueling emissions, technical requirements,and measurement methods of the durability for pollution controlequipment, and onboard diagnostic system (OBD). Onboard refueling vaporrecovery (ORVR) is required, in addition to evaporative emissioncontrol. Evaporative emissions are defined as the hydrocarbon vaporsemitted from the fuel (gasoline) system of a motor vehicle, andincludes: (1) fuel tank breathing losses (diurnal losses), which arehydrocarbon emissions caused by temperature changes in the fuel tank,and (2) hot soak losses, which are hydrocarbon emissions arising fromthe fuel system of a stationary vehicle after a period of driving. Whilethe testing protocol and the emissions limits for the whole vehicletesting are provided in the regulations, there is leeway in theallocation by the vehicle manufacturers for the design limits of thecomponents contributing to the total emissions (e.g., evaporativeemission control canister system, fuel tank walls, hoses, tubing, etc.).Among the allocations, the limit for the evaporative emission controlcanister system is generally set in the fuel system and vehicle designprocesses to be less than 100 mg for the day 2 DBL emissions as part ofthe design balance for meeting the overall vehicle requirements of China6 regulations.

Yet, in the face of the needs for high working capacity performance andfor designing systems for fuel emissions within regulatory limits, thereis a disproportionate increase in the bleed emissions performance as GWCperformance and BWC properties are increased, as is well known in theart. See, e.g., SAE Technical Paper 2001-01-0733 at FIG. 8 (comparisonof DBL emissions data); and U.S. Pat. No. 6,540,815 at Table(comparative and inventive data for 11 BWC versus 15 BWC activatedcarbons).

For satisfying the apparently opposing needs of high working capacityand low DBL emission performance, several approaches have been reported.One approach is to significantly increase the volume of purge gas toenhance desorption of the residue hydrocarbon heel from the adsorbentvolume. See U.S. Pat. No. 4,894,072. This approach, however, has thedrawback of complicating management of the fuel/air mixture to theengine during the purge step and tends to adversely affect tailpipeemissions, and such high levels of purge are simply unavailable forcertain powertrain designs. Though at the cost of design andinstallation, an auxiliary pump may be employed at some location withinthe evaporative emission control system to supplement, assist, oraugment the purge flow or volume, as a means to complement the enginevacuum and to avoid some issues with engine performance and tailpipeemission control when otherwise depending on the engine vacuum alone.

Another approach is to design the canister to have a relatively lowcross-sectional area on the vent-side of the canister, either by theredesign of existing canister dimensions or by the installation of asupplemental vent-side canister of appropriate dimensions. This approachreduces the residual hydrocarbon heel by increasing the intensity ofpurge air. One drawback of such approach is that the relatively lowcross-sectional area imparts an excessive flow restriction to thecanister. See U.S. Pat. No. 5,957,114.

Another approach for increasing the purge efficiency is to heat thepurge air, or a portion of the adsorbent volume having adsorbed fuelvapor, or both. However, this approach increases the complexity ofcontrol system management and poses some safety concerns. See U.S. Pat.Nos. 6,098,601 and 6,279,548.

Another approach is to route the fuel vapor through a fuel-sideadsorbent volume, which is located proximal to the fuel source in thefluid stream, and then at least one subsequent (i.e., vent-side)adsorbent volume, which is located down-stream from the fuel-sideadsorbent, prior to venting to the atmosphere, wherein the fuel-sideadsorbent volume (herein, the initial adsorbent volume”) has a higherisotherm slope, defined as an incremental adsorption capacity, than thesubsequent (i.e., vent-side) adsorbent volume. See U.S. Pat. No.RE38,844. It is notable that U.S. RE38,844 considers the trade-off inDBL bleed emissions performance with BWC as an inevitable consequence ofthe high slope properties of the adsorption isotherms that are presentwith high BWC adsorbents according to the dynamics of vapor andadsorbate concentration gradients along the vapor flow path duringadsorption, purge, and soak cycles. This approach has the drawback ofrequiring multiple adsorbent volumes in-series with varied propertiesfor affording the low emissions, which increases system size,complexity, and cost for design and fabrication.

Another approach, especially useful when only a low level of purge mightbe available, is to route the fuel vapor through at least one subsequent(i.e., vent-side) adsorbent comprising a window of incrementaladsorption capacity, ASTM BWC, a particular g-total BWC capacity, andsubstantially uniform structure that facilitates approximately uniformair and vapor flow distribution across its flow path cross section. SeeU.S. Pat. No. 9,732,649 and U.S. 2016/0271555A1. This approach also hasthe drawback of requiring multiple adsorbent volumes in-series withvaried properties for affording the low emissions, which increasessystem size, complexity, and cost for design and fabrication.

The DBL emissions challenge for high working capacity carbons in theevaporative emission control canister system is recognized in U.S. Pat.No. 9,322,368, where it is asserted that including a low workingcapacity volume towards the vent-side puts an undue burden on the sizeand weight of the canister system for meeting both the high workingcapacity and the maximum allowable DBL emission targets. The alternativesolution taught in U.S. Pat. No. 9,322,368 is to have a volume towardsthe vent-side of the canister system that contains a hollow pellet wherethe volume of pores in the macropore size range 0.05-0.5 micron withinthe pellet structure is controlled in the examples to about 50% of thetotal having a size of 0.05-100 microns. The '368 discloses that with90+% of total macropore volume in pores 0.05-0.5 micron has inferiordesorption performance. These examples were prepared by a grind & bindprocess which included a powder ingredient that decomposed upon processheating in order to create macropore volume.

The dilemma of DBL emissions challenge for high working capacity is alsorecognized in U.S. Pat. No. 9,657,691. Here a solution is taught for amain canister with a large capacity for fuel vapor is combined with asmaller buffer canister with a chamber containing activated carbon withBWC above 13 g/dL, then in-series with a subsequent chamber containingcarbon with BWC between 6 and 10 g/dL that is needed to constrain theemissions to target levels. A further complexity of adding heat to abuffer canister chamber is necessary to achieve target emissions levels.Thus, the dilemma of excessive DBL bleed emissions for high workingcapacity carbons is recognized, in this instance of an auxiliarychamber, and countered by added size and complexity for the canistersystem.

Accordingly, it is desirable to have an evaporative emission controlsystem that is as low cost, simple, and compact as possible for bothproviding the needed GWC and low DBL emission levels. Therefore, a highworking capacity adsorbent that has relatively low DBL emissionproperties would contribute to that end by allowing smaller, lesscostly, and less complicated approaches for system design and operation,both for when normal levels or low levels of purge are available.

SUMMARY

Presently described is an adsorbent material that surprisingly andunexpectedly demonstrates relatively high working capacity and, at thesame time, demonstrates relatively low DBL bleed emission performanceproperties when incorporated into a vehicle emissions canister system.The described material advantageously allows the design of evaporativefuel emission control systems that are lower cost, simpler and morecompact than currently known. As described herein, when tested under astandard vapor cycling protocol, the test canister containing anadsorbent as described herein with a relatively high ASTM BWC,demonstrated lower emissions using standard bleed emission testprocedure (BETP) than current, conventional high ASTM BWC adsorbents.

Thus, in one aspect, the description provides a shaped adsorbentmaterial comprising a relatively high working capacity activatedadsorbent powder bound with a binder, e.g., an organic binder such ascarboxymethyl cellulose (CMC) or an inorganic binder, such as bentoniteclay. In certain embodiments, the shaped adsorbent material comprises anadmixture of a binder and an activated adsorbent powder derived bygrinding an activated adsorbent precursor, wherein the admixture isshaped into a form, and wherein the shaped adsorbent material has anASTM BWC of at least 13 g/dL.

In any of the aspects or embodiments described herein, the activatedadsorbent powder has a powder butane activity (pBACT) of at least 50g/100 g.

In any of the aspects or embodiments described herein, the shapedadsorbent material comprises a ratio of pore volumes of 0.05-1 micron to0.05-100 micron as described herein, e.g., of greater than about 80%.

In any of the aspects or embodiments described herein, the shapedadsorbent material comprises a ratio of pore volumes of 0.05-0.5 micronto 0.05-100 microns as described herein, e.g., that is greater thanabout 50%.

In certain embodiments, the shaped adsorbent material has a ratio ofpore volumes of 0.05-1 micron to 0.05-100 micron as described herein,e.g., of greater than about 80%, a ratio of pore volumes of 0.05-0.5micron to 0.05-100 microns as described herein, e.g., that is greaterthan about 50%, and a ASTM BWC as described herein, e.g., that isgreater than about 13 g/dL.

In any of the aspects or embodiments described herein, the activatedadsorbent precursor is an activated carbon precursor. In any of theaspects or embodiments described herein, the activated carbon precursorhas a butane activity (pBACT) of at least about 50 g/100 g.

In any of the aspects or embodiments described herein, the bindercomprises at least one of an organic binder, an inorganic binder orboth. In certain embodiments, the binder comprises, e.g., an organicbinder such as carboxymethyl cellulose (CMC) or an inorganic binder,such as bentonite clay or both.

In any of the aspects or embodiments described herein, the shapedadsorbent material includes a component selected from the groupconsisting of activated carbon, carbon charcoal, zeolites, clays, porouspolymers, porous alumina, porous silica, molecular sieves, kaolin,titania, ceria, and combinations thereof.

In any of the aspects or embodiments described herein, the shapedadsorbent material comprises activated carbon derived from a materialincluding a member selected from the group consisting of wood, wooddust, wood flour, cotton linters, peat, coal, coconut, lignite,carbohydrates, petroleum pitch, petroleum coke, coal tar pitch, fruitpits, fruit stones, nut shells, nut pits, sawdust, palm, vegetables,synthetic polymer, natural polymer, lignocellulosic material, andcombinations thereof. In any of the aspects or embodiments describedherein, the shaped adsorbent material comprises activated carbon derivedfrom at least one of wood, wood dust, wood flour, cotton linters, peat,coal, coconut, lignite, carbohydrates, petroleum pitch, petroleum coke,coal tar pitch, fruit pits, fruit stones, nut shells, nut pits, sawdust,palm, vegetables or a combination thereof.

In any of the aspects or embodiments described herein, the form ofshaped adsorbent material is selected from a granule, pellet, sphere,honeycomb, monolith, pelletized cylindrical, particulate media ofuniform shape, particulate media of non-uniform shape, structured mediaof extruded form, structured media of poured form, hollow-cylinder,star, twisted spiral, asterisk, configured ribbons, and combinationsthereof.

In any of the aspects or embodiments described herein, the shapedadsorbent material is formed into a structure comprising a matrix withapproximately uniform cell or geometric structure, e.g., a honeycombconfiguration, which permits or facilitates approximately uniform air orvapor flow distribution through the subsequent adsorbent volume.

In another aspect, the disclosure provides an evaporative emissioncontrol canister system comprising at least one fuel-side adsorbentvolume and at least one vent-side adsorbent volume, wherein at least oneof the at least one fuel-side or the at least one vent-side adsorbentvolumes comprises a shaped adsorbent material as described herein.

In any of the aspects or embodiments described herein, the canistersystem comprises one or more vent-side adsorbent volumes having auniform cell structure at or near the end of the fuel vapor flow path.

In any of the aspects or embodiments described herein, the shapedadsorbent material demonstrates two-day diurnal breathing loss (DBL)emissions of 100 mg or less at 315 liters of purge applied after a 40g/hr butane loading step as determined in a 2.1 liter canister asdefined herein (i.e., the “Defined Canister”) by the 2012 CaliforniaBleed Emissions Test Procedure (BETP).

In any of the aspects or embodiments described herein, the system hastwo-day diurnal breathing loss (DBL) emissions of less than 100 mg whentested by the China 6 Type Test Procedure as defined herein.

In certain additional embodiments, the shaped adsorbent material has atwo-day DBL that is at least 10% less than the precursor activatedadsorbent material.

In any of the embodiments described herein, the evaporative emissioncontrol system may further comprise a heating unit.

In an additional aspect, the description provides methods for reducingfuel vapor emissions in an evaporative emission control system, themethod comprising contacting the fuel vapor with an evaporative emissioncontrol system as described herein, comprising a shaped adsorbentmaterial as described herein.

In another aspect, the description provides a shaped adsorbent materialproduced according to the steps comprising: (a) providing an activatedadsorbent precursor; (b) grinding the activated adsorbent precursor to apowder, wherein the powder has a pBACT of at least about 50 g/100 g; (c)admixing the powder with a binder material; and (d) shaping the powderand binder material mixture into a form, wherein the shaped adsorbentmaterial has an ASTM BWC of at least 13 g/dL. In certain embodiments,the shaped adsorbent material further has at least one of: (i) a ratioof pore volumes of 0.05-1 micron to 0.05-100 microns that is greaterthan about 80%, (ii) a ratio of pore volumes of 0.05-0.5 micron to0.05-100 microns that is greater than about 50%, or (iii) a combinationthereof.

The preceding general areas of utility are given by way of example onlyand are not intended to be limiting on the scope of the presentdisclosure and appended claims. Additional objects and advantagesassociated with the compositions, methods, and processes of the presentinvention will be appreciated by one of ordinary skill in the art inlight of the instant claims, description, and examples. For example, thevarious aspects and embodiments of the invention may be utilized innumerous combinations, all of which are expressly contemplated by thepresent description. These additional advantages objects and embodimentsare expressly included within the scope of the present invention. Thepublications and other materials used herein to illuminate thebackground of the invention, and in particular cases, to provideadditional details respecting the practice, are incorporated byreference.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated into and form a partof the specification, illustrate several embodiments of the presentinvention and, together with the description, serve to explain theprinciples of the invention. The drawings are only for the purpose ofillustrating an embodiment of the invention and are not to be construedas limiting the invention. Further objects, features and advantages ofthe invention will become apparent from the following detaileddescription taken in conjunction with the accompanying figures showingillustrative embodiments of the invention, in which:

FIG. 1 is a cross-sectional views of evaporative emission controlcanister systems with many possible combinations of where the inventiveembodiments of the adsorbent may be utilized.

FIG. 2 is a cross-sectional views of evaporative emission controlcanister systems with many possible combinations of where the inventiveembodiments of the adsorbent may be utilized.

FIG. 3 is a cross-sectional views of evaporative emission controlcanister systems with many possible combinations of where the inventiveembodiments of the adsorbent may be utilized.

FIG. 4 is a cross-sectional views of evaporative emission controlcanister systems with many possible combinations of where the inventiveembodiments of the adsorbent may be utilized.

FIG. 5 are DBL emission test data by BETP for comparative examples ofconventional commercial activated carbon adsorbents with a range of ASTMBWC properties.

FIG. 6 are test data DBL emission test data by BETP that includeinventive examples with ASTM BWC properties above 13 g/dL that wereprepared by grind & bind processes.

FIG. 7 are the macropore size distributions for 11-12 g/dL ASTM BWCcomparative commercial examples and for 12.0-12.6 g/dL grind & bindexamples 9 and 10.

FIG. 8 shows the day 2 DBL emissions by BETP as a function of thepercent of total macropores in pores 0.05-0.5 microns in size, for 11-12g/dL ASTM BWC comparative commercial examples and for 12.0-12.6 g/dLASTM BWC grind & bind examples 9 and 10.

FIG. 9 shows the day 2 DBL emissions by BETP as a function of thepercent of total macropores in pores 0.05-1 microns in size, for 11-12g/dL ASTM BWC comparative commercial examples and for 12.0-12.6 g/dLgrind & bind examples 9 and 10.

FIG. 10 are the macropore size distributions for 13+ g/dL ASTM BWCcomparative commercial examples, all produced by shape & activateprocesses.

FIG. 11. are the macropore size distributions for 13+ g/dL ASTM BWCexamples 11 through 16, all prepared by grind & bind processes.

FIG. 12 shows the day 2 DBL emissions by BETP as a function of thepercent of total macropores in pores 0.05-0.5 microns in size, for 13+g/dL ASTM BWC comparative commercial examples and for 13+ g/dL grind &bind examples 11 through 16.

FIG. 13 shows the day 2 DBL emissions by BETP as a function of thepercent of total macropores in pores 0.05-1 microns in size, for 13+g/dL ASTM BWC comparative commercial examples and for 13+ g/dL grind &bind examples 11 through 16.

FIG. 14 shows the day 2 DBL emissions by BETP as a function of the totalmacropores 0.05-100 microns in size in units of cc/g, for comparativecommercial examples and for grind & bind examples 9 through 16.

FIG. 15 shows the day 2 DBL emissions by BETP as a function of the totalmacropores 0.05-100 microns in size in units of cc/cc-pellet, forcomparative commercial examples and for grind & bind examples 9 through16.

FIG. 16 shows the day 2 DBL emissions by BETP as a function of the ratioof the volume of total macropores 0.1-100 microns in size to the volumeof pores less than 0.1 in size, for comparative commercial examples andfor grind & bind examples 9 through 16.

FIG. 17 shows the day 2 DBL emissions by BETP as a function of butaneretentivity, for comparative commercial examples and for grind & bindexamples 9 through 16.

FIG. 18 shows a correlation between the butane activity of the activatedcarbon powder ingredients and the resulting ASTM BWC of the finishedbound pellet for examples 9 through 16.

DETAILED DESCRIPTION

The present disclosure now will be described more fully hereinafter, butnot all embodiments of the disclosure are shown. While the disclosurehas been described with reference to exemplary embodiments, it will beunderstood by those skilled in the art that various changes may be madeand equivalents may be substituted for elements thereof withoutdeparting from the scope of the disclosure. In addition, manymodifications may be made to adapt a particular structure or material tothe teachings of the disclosure without departing from the essentialscope thereof.

The drawings accompanying the application are for illustrative purposesonly. They are not intended to limit the embodiments of the presentapplication. Additionally, the drawings are not drawn to scale. Elementscommon between figures may retain the same numerical designation.

Where a range of values is provided, it is understood that eachintervening value between the upper and lower limit of that range andany other stated or intervening value in that stated range isencompassed within the invention. The upper and lower limits of thesesmaller ranges may independently be included in the smaller ranges isalso encompassed within the invention, subject to any specificallyexcluded limit in the stated range. Where the stated range includes oneor both of the limits, ranges excluding either both of those includedlimits are also included in the invention.

The following terms are used to describe the present invention. Ininstances where a term is not specifically defined herein, that term isgiven an art-recognized meaning by those of ordinary skill applying thatterm in context to its use in describing the present invention.

The articles “a” and “an” as used herein and in the appended claims areused herein to refer to one or to more than one (i.e., to at least one)of the grammatical object of the article unless the context clearlyindicates otherwise. By way of example, “an element” means one elementor more than one element.

The phrase “and/or,” as used herein in the specification and in theclaims, should be understood to mean “either or both” of the elements soconjoined, i.e., elements that are conjunctively present in some casesand disjunctively present in other cases. Multiple elements listed with“and/or” should be construed in the same fashion, i.e., “one or more” ofthe elements so conjoined. Other elements may optionally be presentother than the elements specifically identified by the “and/or” clause,whether related or unrelated to those elements specifically identified.Thus, as a non-limiting example, a reference to “A and/or B”, when usedin conjunction with open-ended language such as “comprising” can refer,in one embodiment, to A only (optionally including elements other thanB); in another embodiment, to B only (optionally including elementsother than A); in yet another embodiment, to both A and B (optionallyincluding other elements); etc.

As used herein in the specification and in the claims, “or” should beunderstood to have the same meaning as “and/or” as defined above. Forexample, when separating items in a list, “or” or “and/or” shall beinterpreted as being inclusive, i.e., the inclusion of at least one, butalso including more than one, of a number or list of elements, and,optionally, additional unlisted items. Only terms clearly indicated tothe contrary, such as “only one of” or “exactly one of,” or, when usedin the claims, “consisting of,” will refer to the inclusion of exactlyone element of a number or list of elements. In general, the term “or”as used herein shall only be interpreted as indicating exclusivealternatives (i.e., “one or the other but not both”) when preceded byterms of exclusivity, such as “either,” “one of,” “only one of,” or“exactly one of.”

In the claims, as well as in the specification above, all transitionalphrases such as “comprising,” “including,” “carrying,” “having,”“containing,” “involving,” “holding,” “composed of,” and the like are tobe understood to be open-ended, i.e., to mean including but not limitedto. Only the transitional phrases “consisting of” and “consistingessentially of” shall be closed or semi-closed transitional phrases,respectively, as set forth in the 10 United States Patent Office Manualof Patent Examining Procedures, Section 2111.03.

As used herein in the specification and in the claims, the phrase “atleast one,” in reference to a list of one or more elements, should beunderstood to mean at least one element selected from anyone or more ofthe elements in the list of elements, but not necessarily including atleast one of each and every element specifically listed within the listof elements and not excluding any combinations of elements in the listof elements. This definition also allows that elements may optionally bepresent other than the elements specifically identified within the listof elements to which the phrase “at least one” refers, whether relatedor unrelated to those elements specifically identified. Thus, as anonlimiting example, “at least one of A and B” (or, equivalently, “atleast one of A or B,” or, equivalently “at least one of A and/or B”) canrefer, in one embodiment, to at least one, optionally including morethan one, A, with no B present (and optionally including elements otherthan B); in another embodiment, to at least one, optionally includingmore than one, B, with no A present (and optionally including elementsother than A); in yet another embodiment, to at least one, optionallyincluding more than one, A, and at least one, optionally including morethan one, B (and optionally including other elements); etc. It shouldalso be understood that, unless clearly indicated to the contrary, inany methods claimed herein that include more than one step or act, theorder of the steps or acts of the method is not necessarily limited tothe order in which the steps or acts of the method are recited.

As used herein, the terms “fluid,” “gas” or “gaseous” and “vapor” or“vaporous” are used in a general sense and, unless the context indicatesotherwise, are intended to be interchangeable.

As used herein, unless the context indicates otherwise, the term “shapedadsorbent” or “shaped adsorbent material” is intended to refer to a highactivity or high BWC activated adsorbent material that has been groundto a powder, bound using a binder and shaped as described herein (i.e.,“grind and bind”), and that provides the described and claimed porosityand system advantages. The above terms are to be distinguished from thedescription's reference to “shaped and activated” materials, whichspecifically refers to a precursor carbon material that was bound andshaped prior to activation.

U.S. patent application Ser. No. 15/656,643 titled: ParticulateAdsorbent Material and Methods of Making the Same, filed 21 Jul. 2017;U.S. Patent Publication US 2016/0271555A; U.S. Pat. Nos. 9,732,649; and6,472,343 are hereby incorporated by reference in their entirety for allpurposes.

Described herein are shaped adsorbent materials and systems thatsurprisingly and unexpectedly demonstrate a high working capacityadsorbent with relatively low DBL bleed emission performance properties,including at relatively low purge volumes, which allows the design ofevaporative fuel emission control systems that are lower cost, simpler,and more compact than those currently available.

Thus, in one aspect, the description provides a shaped adsorbentmaterial comprising an admixture of a binder and an activated adsorbentpowder derived by grinding an activated adsorbent precursor, wherein theadmixture is shaped into a form, and wherein the shaped adsorbentmaterial has an ASTM BWC property of at least about 13 g/dL.

In certain embodiments, the shaped adsorbent material as describedherein has an ASTM BWC that is greater than about 13 g/dL. In certainembodiments, the shaped adsorbent material as described herein has anASTM BWC of greater than about 13 g/dL, 14 g/dL, 15 g/dL, 16 g/dL, 17g/dL, 18 g/dL, 19 g/dL, 20 g/dL, 21 g/dL, 22 g/dL, 23 g/dL, 24 g/dL, 25g/dL, or more than 25 g/dL, or from about 13 g/dL to about 40 g/dL, fromabout 13 g/dL to about 30 g/dL, or from about 13 g/dL to about 20 g/dL,and including all overlapping ranges, subsumed ranges and values inbetween.

Without being bound by any particular theory, the unexpectedly high BWCand low DBL of the described shaped adsorbent material described hereinappears correlated with selection of a precursor material with very highbutane activity. Therefore, in any aspect or embodiment describedherein, the activated adsorbent powder, e.g., activated carbon powder,has a butane activity (pBACT) of at least about 50 g/100 g. In certainembodiments, the pBACT of the activated adsorbent precursor is at leastabout 50 g/100 g, 55 g/100 g, 60 g/100 g, 65 g/100 g, 70 g/100 g, 75g/100 g, 80 g/100 g, 85 g/100 g, 90 g/100 g, 95 g/100 g or moreincluding all values in between. In certain embodiments, the pBACT ofthe activated adsorbent powder, e.g., activated carbon powder, is fromabout 50 g/100 g to about 95 g/100 g, from about 50 g/100 g to about 90g/100 g, from about 50 g/100 g to about 85 g/100 g, from about 50 g/100g to about 80 g/100 g, from about 50 g/100 g to about 75 g/100 g, fromabout 50 g/100 g to about 70 g/100 g, from about 50 g/100 g to about 65g/100 g, about 50 g/100 g to about 60 g/100 g, and including alloverlapping ranges, subsumed ranges and values in between.

Generally, the larger the surface area of the activated carbon, thegreater its adsorption capacity. The available surface area of activatedcarbon is dependent on its pore volume. Since the surface area per unitvolume decreases as individual pore size increases, large surface areagenerally is maximized by maximizing the number of pores of very smalldimensions and/or minimizing the number of pores of very largedimensions. Pore sizes are defined herein as micropores (pore width <1.8nm), mesopores (pore width=1.8-50 nm), and macropores (pore width >50nm, and nominally 50 nm-100 microns). Mesopores may be further dividedbetween small mesopores (pore width=1.8-5 nm) and large mesopores (porewidth=5-50 nm).

In certain embodiments, the shaped adsorbent material as describedherein has a ratio of pore volumes of 0.05-1 micron to 0.05-100 micronthat is greater than about 80%, or about 90%, including all values inbetween. In certain embodiments, the ratio of pore volumes of 0.05-1micron to 0.05-100 micron is about 80%, about 81%, about 82%, about 83%,about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%,about 97%, about 98%, or about 99% including all values in between. Incertain embodiments, the ratio of pore volumes of 0.05-1 micron to0.05-100 micron is from 80-85%, 80-90%, 80-95%, 80-99%, 82-85%, 82-90%,82-95%, 82-99%, 85-90%, 85-95%, 85-99%, 90-95%, or 90-99%, and includingall overlapping ranges, subsumed ranges and values in between.

In certain embodiments, the shaped adsorbent material as describedherein has a ratio of pore volumes of 0.05-0.5 micron to 0.05-100microns that is greater than about 50%, greater than about 60%, greaterthan about 70%, greater than about 80%, or greater than about 90%,including all values in between. In certain embodiments, the ratio ofpore volumes of 0.05-0.5 micron to 0.05-100 microns is about 50%, about51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%,about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about64%, about 65%, about 66%, about 67%, about 68%, about 69%, about 70%,about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%,about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%,about 97%, about 98%, or about 99%. In certain embodiments, the ratio ofpore volumes of 0.05-0.5 micron to 0.05-100 microns is from about50-99%, about 50-95%, about 50-90%, about 50-85%, about 50-80%, about50-75%, about 50-70%, about 50-65%, about 50-60%, about 50-55%, about55-99%, about 55-95%, about 55-90%, about 55-85%, about 55-80%, about55-75%, about 55-70%, about 55-65%, about 55-60%, about 60-99%, about60-95%, about 60-90%, about 60-85%, about 60-80%, about 60-75%, about60-70%, about 60-65%, about 65-99%, about 65-95%, about 65-90%, about65-85%, about 65-80%, about 65-75%, about 65-70%, about 70-99%, about70-95%, about 70-90%, about 70-85%, about 70-80%, about 70-75%, about75-99%, about 75-95%, about 75-90%, about 75-85%, about 75-80%, about80-99%, about 80-95%, 80-90%, about 80-85%, about 85-99%, about 85-95%,about 85-90%, about 90-99%, or about 90-95% and including alloverlapping ranges, subsumed ranges and values in between.

In certain embodiments, the description provides a shaped adsorbentmaterial comprising a ratio of pore volumes of 0.05-1 micron to 0.05-100micron as described herein, e.g., of greater than about 80%, greaterthan about 90% or more, a ratio of pore volumes of 0.05-0.5 micron to0.05-100 microns as described herein, e.g., that is greater than about50%, greater than about 60%, greater than about 70%, greater than about80%, or greater than about 90%, and a ASTM BWC as described herein,e.g., that is greater than about 13 g/dL, or 14 g/dL, or 15 g/dL, or 16g/dL, or 17 g/dL, or 18 g/dL, or 19 g/dL, or 20 g/dL, or 21 g/dL, or 22g/dL, or 23 g/dL, or 24 g/dL, or 25 g/dL, or more than 25 g/dL, or fromabout 13 g/dL to about 40 g/dL, or from about 13 g/dL to about 30 g/dL,or from about 13 g/dL to about 20 g/dL, and including all values inbetween.

In certain embodiments, the activated adsorbent powder as describedherein is derived by grinding an activated carbon precursor, wherein theactivated carbon precursor is derived from at least one of wood, wooddust, wood flour, cotton linters, peat, coal, coconut, lignite,carbohydrates, petroleum pitch, petroleum coke, coal tar pitch, fruitpits, fruit stones, nut shells, nut pits, sawdust, palm, vegetables,synthetic polymer, natural polymer, lignocellulosic material, or acombination thereof. In any of the aspects or embodiments describedherein, the activated carbon precursor has a butane activity (pBACT) asdescribed herein.

In any of the aspects or embodiments described herein, the shapedadsorbent material includes a component selected from the groupconsisting of activated carbon, carbon charcoal, zeolites, clays, porouspolymers, porous alumina, porous silica, molecular sieves, kaolin,titania, ceria, and combinations thereof.

In any of the aspects or embodiments, the adsorbent material comprises,e.g., a high activity (i.e., high working capacity) activated carbonpowder bound with one or more binders, e.g., an organic binder such ascarboxymethyl cellulose (CMC) or an inorganic binder, such as bentoniteclay, or a combination of binders. In certain embodiments, the bindercomprises at least one of a clay or a silicate material. For example, incertain embodiments, the binder is at least one of zeolite clay,bentonite clay, montmorillonite clay, illite clay, French green clay,pascalite clay, redmond clay, terramin clay, living clay, Fuller's Earthclay, ormalite clay, vitallite clay, rectorite clay, cordierite, ballclay, kaolin or a combination thereof.

Additional potential binders include, thermosetting binders and hot-meltbinders. Thermosetting binders are compositions based on thermosettingresins which are liquid or solid at ambient temperature and inparticular those of urea-formaldehyde, melamine-urea-formaldehyde orphenol-formaldehyde type, resins of melamine-urea-formaldehyde typebeing preferred as well as emulsions of thermosetting (co)polymers inthe latex foam. Crosslinking agents can be incorporated in the mixture.Mention may be made, as example of crosslinking agents, of ammoniumchloride. Hot-melt binders are generally solid at ambient temperatureand are based on resins of hot-melt type. Use may also be made, asbinders, of pitch, tar or any other known binder.

In any of the embodiments described herein, the binder can comprise anaqueous soluble binders (e.g., polar binders), including but not limitedto cellulosic binders and related esters, including methyl and ethylcellulose and their derivatives, e.g., carboxymethyl cellulose (CMC),ethylcellulose, ethyl methyl cellulose, hydroxyethyl cellulose,hydroxypropyl cellulose (HPC), hydroxyethyl methyl cellulose,hydroxypropyl methyl cellulose (HPMC), ethyl hydroxyethyl cellulose,crystalline salts of aromatic sulfonates, polyfurfuryl alcohol,polyester, polyepoxide or polyurethane polymers etc.

In any of the embodiments described herein, the binder can comprise annon-aqueous binder, such as clays, phenolic resins, lignins,linosulfonates, polyacrylates, poly vinyl acetates, polyvinylidenechloride (PVDC), ultra-high molecular weight polyethylene (UHMWPE),etc., fluoropolymer, e.g., polyvinylidene difluoride (PVDF),polyvinylidene dichloride (PVDC), a polyamide (e.g., Nylon-6,6′ orNylon-6), a high-performance plastic (e.g. polyphenylene sulfide),polyketones, polysulfones, and liquid crystal polymers, copolymers witha fluoropolymer (e.g. poly(vinylidene difluoride)),polytetrafluoroethylene (PTFE), fluorinated ethylene propylene, orperfluoroalkoxy alkanes), copolymers with a polyamide (e.g., Nylon-6,6′or Nylon-6), a copolymer with a polyimide, a copolymer with ahigh-performance plastic (e.g. polyphenylene sulfide) or a combinationthereof.

In certain embodiments, the shaped adsorbent material as describedherein is produced from the binder crosslinking of a ground precursoractivated carbon material, wherein the ground activated carbon materialis in the form of a powder. For example, in certain embodiments, theshaped adsorbent material as described herein is produced by taking apowdered activated carbon material and applying the crosslinking bindertechnology of U.S. Pat. No. 6,472,343.

Different types of shaped carbon bodies have been demonstrated with thisinventive polymeric binder technology. These include (but are notlimited to) granules, cylindrical pellets, spheres, sheets, ribbons,trilobes, and honeycombs. In principle, any desired shape of carbon bodycan be formed with a proper shaping device. So, shapes such asmonoliths, blocks, and other modular forms are envisioned as well. Thisbinder technology is applicable to virtually all varieties of activatedcarbons, including those made from different precursor materials such aswood, coal, coconut, nutshell, and olive pit prepared by acid, alkali,or thermal activation.

Alternatively, or in combination, an inorganic binder may be used. Theinorganic binder may be a clay or a silicate material. For example, thebinder of the low retentivity particulate adsorbent may be at least oneof Zeolite clay, Bentonite clay, Montmorillonite clay, Illite clay,French Green clay, Pascalite clay, Redmond clay, Terramin clay, Livingclay, Fuller's Earth clay, Ormalite clay, Vitallite clay, Rectoriteclay, Cordierite, ball clay, kaolin or a combination thereof.

The binder as described herein for use in combination with the powderedactivated carbon material can work with a variety of mixing, shaping andheat treating equipment. Different mixing devices such as low shearmullers, medium shear paddle mixers and high shear pin mixers have beendemonstrated to produce a material that is suitable for subsequentshaping. Shaping devices such as auger extruders, ram extruders,granulators, roller pelletizers, spheronizers, and tableting presses aresuitable, depending on the applications. Drying and curing of the wetcarbon bodies can be carried out at temperatures below 270° C. with avariety of different devices, such as a convection tray oven, avibrating fluid bed dryer, and a rotary kiln. In contrast, highertemperatures of about 500-1000° C. can be used for thermal treatment ofclay-bound and phenolic resin-bound carbons, usually using a rotarykiln.

In any of the embodiments described herein, the form of adsorbentmaterial is selected from the group consisting of granular, pellet,spherical, pelletized cylindrical, particulate media of uniform shape,particulate media of non-uniform shape, structured media of extrudedform, structured media of poured form, hollow-cylinder, star, twistedspiral, asterisk, configured ribbons, and combinations thereof.

In certain additional embodiments, the adsorbent material is formed intoa structure comprising a matrix with approximately uniform cell orgeometric structure, e.g., a honeycomb configuration, which permits orfacilitates approximately uniform air or vapor flow distribution throughthe subsequent adsorbent volume. In further embodiments, the adsorbentmaterial is formed into a structure that includes a combination of anyof the foregoing.

The adsorbent material may include any one or more of the abovefeatures, which can be combined in any number of ways according to thepresent description, and are expressly contemplated herein.

In another aspect, the description provides a method for making a shapedadsorbent material and/or a shaped adsorbent material produced accordingto the steps comprising: (a) providing an activated adsorbent precursor,e.g., an activated carbon precursor as described herein such asactivated carbon; (b) grinding the activated adsorbent precursor to apowder, wherein the powder has a pBACT of at least about 50 g/100 g; (c)admixing the powder with a binder material; and (d) shaping the powderand binder material admixture into a form, wherein the shaped adsorbentmaterial has an ASTM BWC as described herein, e.g., at least 13 g/dL. Incertain embodiments, the shaping step is performed by extruding theadmixture of step (c). In certain embodiments, the extrusion isperformed at a relative humidity of from about 50% to about 75%, or fromabout 50% to about 65%.

In certain embodiments, the pBACT of the activated adsorbent powder,e.g., activated carbon powder, is from about 50 g/100 g to about 95g/100 g, from about 50 g/100 g to about 90 g/100 g, from about 50 g/100g to about 85 g/100 g, from about 50 g/100 g to about 80 g/100 g, fromabout 50 g/100 g to about 75 g/100 g, from about 50 g/100 g to about 70g/100 g, from about 50 g/100 g to about 65 g/100 g, about 50 g/100 g toabout 60 g/100 g, and including all overlapping ranges, subsumed rangesand values in between.

In certain embodiments, the shaped adsorbent has an ASTM BWC that isgreater than about 13 g/dL, or 14 g/dL, or 15 g/dL, or 16 g/dL, or 17g/dL, or 18 g/dL, or 19 g/dL, or 20 g/dL, or 21 g/dL, or 22 g/dL, or 23g/dL, or 24 g/dL, or 25 g/dL, or more than 25 g/dL, or from about 13g/dL to about 40 g/dL, or from about 13 g/dL to about 30 g/dL, or fromabout 13 g/dL to about 20 g/dL, and including all overlapping ranges,subsumed ranges and values in between.

In certain embodiments, the method comprises an additional step ofdrying the shaped adsorbent material. In certain embodiments, the methodincludes tumbling the shaped adsorbent material. In certain embodiments,the tumbling step is performed prior to drying. In certain embodiments,the tumbling step is performed subsequent to drying. In certainembodiments, the tumbling step is performed for at least 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 minutes or more.Without being bound by any particular theory, it is hypothesized thattumbling dimples the material and increases the density.

In certain embodiments, the shaped adsorbent material further has atleast one of: (i) a ratio of pore volumes of 0.05-1 micron to 0.05-100microns that is as described herein, e.g., greater than about 80%, (ii)a ratio of pore volumes of 0.05-0.5 micron to 0.05-100 microns that isas described herein, e.g., greater than about 50%, or (iii) acombination thereof. In certain embodiments, the shaping step isperformed by extrusion.

In certain additional embodiments, the method includes step (e) ofdrying, curing or calcining the shaped adsorbent material. In certainembodiments the drying, curing or calcining step is performed for fromabout 30 minutes to about 20 hours. In certain embodiments, the dryingcuring or calcining step is performed for about 1, about 2, about 3,about 4, about 5, about 6, about 7, about 8, about 9, about 10, about11, about 12, about 13, about 14, about 15, about 16, about 17, about18, about 19, or about 20 hours, including all values in between. Incertain embodiments, the drying, curing or calcining step is performedat a temperature ranging from about 100° C. to about 650° C. In certainembodiments, the drying, curing or calcining step is performed at atemperature of about 100° C., about 110° C., about 120° C., about 130°C., about 140° C., about 150° C., about 160° C., about 170° C., about180° C., about 190° C., about 200° C., about 250° C., about 300° C.,about 350° C., about 400° C., about 450° C., about 500° C., about 550°C., about 600° C., about 650° C., about 700° C., or about 750° C., orabout 800° C., or about 850° C., or about 900° C., or about 950° C., orabout 1000° C., or about 1050° C., or about 1100° C.

In any of the aspects or embodiments described herein the activatedadsorbent powder, e.g., activated carbon powder, is included in anamount of from 75 wt % to about 99 wt %, or from about 80 wt % to about99 wt %, including all ranges overlapping or subsumed, and all values inbetween. In any of the aspects or embodiments described herein theactivated adsorbent powder, e.g., activated carbon powder, is includedin an amount of about 75 wt %, about 76 wt %, about 77 wt %, about 78 wt%, about 79 wt %, about 80 wt %, about 81 wt %, about 82 wt %, about 83wt %, about 84 wt %, about 85 wt %, about 86 wt %, about 87 wt %, about88 wt %, about 89 wt %, about 90 wt %, about 91 wt %, about 92 wt %,about 93 wt %, about 94 wt %, about 95 wt %, about 96 wt %, about 97 wt%, about 98 wt %, or about 99 wt % including all values in between.

In any of the aspects or embodiments described herein, the binder, e.g.,cellulosic or clay binder, is included in an amount of from about 0.05wt % to about 25 wt % to about 1 wt %. In any of the aspects orembodiments described herein, the binder, e.g., clay binder, is includedin an amount of about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %,about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %,about 10 wt %, about 11 wt %, about 12 wt %, 13 wt %, about 14 wt %,about 15 wt %, about 16 wt %, about 17 wt %, about 18 wt %, about 19 wt%, about 20 wt %, about 21 wt %, about 22 wt %, about 23 wt %, about 24wt %, or about 25 wt % including all values in between.

In certain embodiments, the amount of binder is less than about 8 wt %,for example from about 0.05 wt % to about 8 wt %, from about 0.1 wt % toabout 8 wt %, from about 0.5 wt % to about 8 wt %, from about 1.0 wt %to about 8 wt %, from about 1.5 wt % to about 8 wt %, from about 2.0 wt% to about 8 wt %, from about 2.5 wt % to about 8 wt %, from about 3.0wt % to about 8 wt %, from about 3.5 wt % to about 8 wt %, or from about4.0 wt % to about 8 wt % including all values in between. In certainembodiments, the binder is CMC and is present in an amount of less thanabout 8 wt %, for example from about 0.05 wt % to about 8 wt %, fromabout 0.1 wt % to about 8 wt %, from about 0.5 wt % to about 8 wt %,from about 1.0 wt % to about 8 wt %, from about 1.5 wt % to about 8 wt%, from about 2.0 wt % to about 8 wt %, from about 2.5 wt % to about 8wt %, from about 3.0 wt % to about 8 wt %, from about 3.5 wt % to about8 wt %, or from about 4.0 wt % to about 8 wt %, including all values inbetween. It was observed that at the claimed amount of binder, theresulting shaped adsorbents provided surprisingly and unexpectedlyadvantageous BWC as well as relatively low DBL.

In certain embodiments, the amount of binder is from about 10 wt % toabout 35 wt %, for example from about 10 wt % to about 30 wt %, fromabout 10 wt % to about 25 wt %, from about 10 wt % to about 20 wt %, orfrom about 10 wt % to about 15 wt %, including all values in between. Incertain embodiments, the binder is bentonite clay and is present in anamount of from about 10 wt % to about 35 wt %, for example from about 10wt % to about 30 wt %, from about 10 wt % to about 25 wt %, from about10 wt % to about 20 wt %, or from about 10 wt % to about 15 wt %,including all values in between. It was observed that at the claimedamount of binder, the resulting shaped adsorbents provided surprisinglyand unexpectedly advantageous BWC as well as relatively low DBL.

In certain embodiments, the shaped adsorbent material has a ratio ofpore volumes of 0.05-1 micron to 0.05-100 micron of greater than about80%, greater than about 90% or more. In additional embodiments, theshaped adsorbent has a ratio of pore volumes of 0.05-0.5 micron to0.05-100 microns of greater than about 50%, greater than about 60%,greater than about 70%, greater than about 80%, or greater than about90%. In additional embodiments, the shaped adsorbent has an ASTM BWCthat is greater than about 13 g/dL, or 14 g/dL, or 15 g/dL, or 16 g/dL,or 17 g/dL, or 18 g/dL, or 19 g/dL, or 20 g/dL, or 21 g/dL, or 22 g/dL,or 23 g/dL, or 24 g/dL, or 25 g/dL, or more than 25 g/dL, or from about13 g/dL to about 40 g/dL, or from about 13 g/dL to about 30 g/dL, orfrom about 13 g/dL to about 20 g/dL, and including all overlappingranges, subsumed ranges and values in between. In certain embodiments,the activated adsorbent precursor is an activated carbon precursor. Incertain embodiments, the binder material is as described herein. Inanother embodiment, the shaped adsorbent is in any form describedherein.

In certain embodiments, when the shaped adsorbent material as describedherein is the fill in a 2.1 liter test canister having the dimensions asdescribed herein (i.e., the “Defined Canister”), the Defined Canisterdemonstrates two-day DBL bleed emissions performance (second day diurnalbreathing loss (DBL) emissions) of about 100 mg or less, about 90 mg orless, about 80 mg or less, about 70 mg or less, about 60 mg or less,about 50 mg or less, about 40 mg or less, about 30 mg or less, about 20mg or less, or about 10 mg or less with 315 liters (i.e., 150 BV) ofpurge applied after a 40 g/hr butane loading step as determined by the2012 BETP. In certain embodiments, when the shaped adsorbent material asdescribed herein is the fill in the Defined Canister, the DefinedCanister demonstrates two-day DBL bleed emissions performance of fromabout 10 mg to about 100 mg, from about 10 mg to about 90 mg, from about10 mg to about 80 mg, from about 10 mg to about 70 mg, from about 10 mgto about 60 mg, from about 10 mg to about 50 mg, from about 10 mg toabout 40 mg, from about 10 mg to about 30 mg, from about 10 mg to about20 mg, from about 15 mg to about 100 mg, from about 15 mg to about 90mg, from about 15 mg to about 80 mg, from about 15 mg to about 70 mg,from about 15 mg to about 60 mg, from about 15 mg to about 50 mg, fromabout 15 mg to about 40 mg, from about 15 mg to about 30 mg, from about15 mg to about 20 mg, from about 20 mg to about 100 mg, from about 20 mgto about 90 mg, from about 20 mg to about 80 mg, from about 20 mg toabout 70 mg, from about 20 mg to about 60 mg, from about 20 mg to about50 mg, from about 20 mg to about 40 mg, from about 20 mg to about 30 mg,from about 30 mg to about 100 mg, from about 30 mg to about 90 mg, fromabout 30 mg to about 80 mg, from about 30 mg to about 70 mg, from about30 mg to about 60 mg, from about 30 mg to about 50 mg, from about 30 mgto about 40 mg, from about 40 mg to about 100 mg, from about 40 mg toabout 90 mg, from about 40 mg to about 80 mg, from about 40 mg to about70 mg, from about 40 mg to about 60 mg, from about 40 mg to about 50 mg,from about 50 mg to about 100 mg, from about 50 mg to about 90 mg, fromabout 50 mg to about 80 mg, from about 50 mg to about 70 mg, from about50 mg to about 60 mg, from about 60 mg to about 100 mg, from about 60 mgto about 90 mg, from about 60 mg to about 80 mg, from about 60 mg toabout 70 mg, from about 70 mg to about 100 mg, from about 70 mg to about90 mg, from about 70 mg to about 80 mg, from about 80 mg to about 100mg, from about 80 mg to about 90 mg, or from about 90 mg to about 100mg, including all values and ranges overlapping, subsumed, and inbetween with 315 liters (i.e., 150 BV) of purge applied after a 40 g/hrbutane loading step as determined by the 2012 BETP.

In certain embodiments, the shaped adsorbent as tested as the volumefill in a 2.1 liter canister as described herein (i.e., the “DefinedCanister”) has a two-day diurnal breathing loss (DBL) emissions of nomore than 100 mg at 150 bed volumes (BV) of purge applied after the 40g/hr butane loading step, as determined by the 2012 California BleedEmissions Test Procedure (BETP), or a DBL of no more than 90 mg at 150bed volumes of purge applied after the 40 g/hr butane loading step, asdetermined by the 2012 BETP, or a DBL of no more than 80 mg at 150 bedvolumes of purge applied after the 40 g/hr butane loading step, asdetermined by the 2012 BETP, or a DBL of no more than 70 mg at 150 bedvolumes of purge applied after the 40 g/hr butane loading step, asdetermined by the 2012 BETP, or a DBL of no more than 60 mg at 150 bedvolumes of purge applied after the 40 g/hr butane loading step, asdetermined by the 2012 BETP, or a DBL of no more than 50 mg at 150 bedvolumes of purge applied after the 40 g/hr butane loading step, asdetermined by the 2012 BETP, or a DBL of no more than 40 mg at 150 bedvolumes of purge applied after the 40 g/hr butane loading step, asdetermined by the 2012 BETP, or a DBL of no more than 30 mg at 150 bedvolumes of purge applied after the 40 g/hr butane loading step, asdetermined by the 2012 BETP, or a DBL of no more than 20 mg at 150 bedvolumes of purge applied after the 40 g/hr butane loading step, asdetermined by the 2012 BETP, including all values in between.

In certain additional embodiments, a canister comprising the shapedadsorbent as described herein as tested as the volume fill in a 2.1liter canister as described herein (i.e., the “Defined Canister”) has antwo-day DBL at 315 L or 150 BV of purge applied after the 40 g/hr butaneloading step, as determined by the 2012 BETP that is reduced by about10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%,about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about75%, about 80%, about 85%, about 90%, about 95% or more as compared tothe precursor activated adsorbent material.

In certain additional embodiments, a canister comprising the shapedadsorbent as described herein as tested as the volume fill in a 2.1liter canister as described herein (i.e., the “Defined Canister”) has antwo-day DBL at 315 L or 150 BV of purge applied after the 40 g/hr butaneloading step, as determined by the 2012 BETP that is reduced by fromabout 10% to about 95%, from about 10% to about 90%, from about 10% toabout 85%, from about 10% to about 80%, from about 10% to about 75%,from about 10% to about 70%, from about 10% to about 65%, from about 10%to about 60%, from about 10% to about 55%, from about 10% to about 50%,from about 10% to about 45%, from about 10% to about 40%, from about 10%to about 35%, from about 10% to about 30%, from about 10% to about 25%,from about 10% to about 20%, from about 10% to about 15%, from about 20%to about 95%, from about 20% to about 90%, from about 20% to about 85%,from about 20% to about 80%, from about 20% to about 75%, from about 20%to about 70%, from about 20% to about 65%, from about 20% to about 60%,from about 20% to about 55%, from about 20% to about 50%, from about 20%to about 45%, from about 20% to about 40%, from about 20% to about 35%,from about 20% to about 30%, from about 20% to about 25%, from about 30%to about 95%, from about 30% to about 90%, from about 30% to about 85%,from about 30% to about 80%, from about 30% to about 75%, from about 30%to about 70%, from about 30% to about 65%, from about 30% to about 60%,from about 30% to about 55%, from about 30% to about 50%, from about 30%to about 45%, from about 30% to about 40%, from about 30% to about 35%,from about 40% to about 95%, from about 40% to about 90%, from about 40%to about 85%, from about 40% to about 80%, from about 40% to about 75%,from about 40% to about 70%, from about 40% to about 65%, from about 40%to about 60%, from about 40% to about 55%, from about 40% to about 50%,from about 40% to about 45%, from about 50% to about 95%, from about 50%to about 90%, from about 50% to about 85%, from about 50% to about 80%,from about 50% to about 75%, from about 50% to about 70%, from about 50%to about 65%, from about 50% to about 60%, or from about 50% to about55% as compared to the precursor activated adsorbent material, includingall values and ranges overlapping, subsumed, and in between.

In another aspect, the disclosure provides an evaporative emissioncontrol canister system comprising at least one adsorbent volumeincluding a shaped adsorbent volume as described herein. In certainembodiments, the shaped adsorbent volume comprises an admixture of abinder and an activated adsorbent powder derived by grinding anactivated adsorbent precursor, wherein the admixture is shaped into aform, and wherein the shaped adsorbent material has an ASTM BWC of atleast 13 g/dL. In certain embodiments, the activated adsorbent powderhas as butane activity (pBACT) of at least about 50 g/100 g. In certainembodiments, the shaped adsorbent material has at least one of: (i) aratio of pore volumes of 0.05-1 micron to 0.05-100 microns that isgreater than about 80%, (ii) a ratio of pore volumes of 0.05-0.5 micronto 0.05-100 microns that is greater than about 50%, or (iii) acombination thereof.

In certain aspects, the evaporative emission control canister systemcomprises at least one fuel-side adsorbent volume and at least onesubsequent (i.e., vent-side) adsorbent volume, wherein at least one ofthe at least one fuel-side adsorbent volume or at least one subsequentadsorbent volume includes a shaped adsorbent material as describedherein.

In any of the aspects or embodiments described herein, the evaporativeemission control canister system has a two-day diurnal breathing loss(DBL) emissions of 100 mg or less with no more than 315 liters of purgeapplied after a 40 g/hr butane loading step as determined by the 2012California Bleed Emissions Test Procedure (BETP).

In certain embodiments, the evaporative emission control canister systemhas a two-day diurnal breathing loss (DBL) emissions of no more thanabout 100 mg, no more than about 95 mg, no more than about 90 mg, nomore than about 85 mg, no more than about 80 mg, no more than about 75mg, no more than about 70 mg, no more than about 65 mg, no more thanabout 60 mg, no more than about 55 mg, no more than about 50 mg, no morethan about 45 mg, no more than about 40 mg, no more than about 35 mg, nomore than about 30 mg, no more than about 25 mg, no more than about 20mg, no more than about 15 mg or no more than about 10 mg at no more thanabout 315 liters, no more than about 310 liters, no more than about 300liters, no more than about 290 liters, no more than about 280 liters, nomore than about 270 liters, no more than about 260 liters, no more thanabout 250 liters, no more than about 240 liters, no more than about 230liters, no more than about 220 liters, no more than about 210 liters, nomore than about 200 liters, no more than about 190 liters, no more thanabout 180 liters, no more than about 170 liters, no more than about 160liters, no more than about 150 liters, no more than about 140 liters, nomore than about 130 liters, no more than about 120 liters, no more thanabout 110 liters, no more than about 100 liters, no more than about 90liters, or no more than about 80 liters of purge applied after a 40 g/hrbutane loading step as determined by the 2012 California Bleed EmissionsTest. In certain embodiments, the amount of purge volume providing theabove two-day DBL emissions as determined by the 2012 BETP is from about50 liters to about 315 liters, from about 75 liters to about 315 liters,from about 100 liters to about 315 liters, from about 125 liters toabout 315 liters, from about 150 liters to about 315 liters, from about175 liters to about 315 liters, from about 200 liters to about 315liters, from about 210 liters to about 315 liters, from about 220 litersto about 315 liters, from about 230 liters to about 315 liters, fromabout 240 liters to about 315 liters, or from about 250 liters to about315 liters, including all values and ranges overlapping, subsumed, andin between.

In certain embodiments, the evaporative emission control canister systemhas a two-day diurnal breathing loss (DBL) emissions of no more thanabout 100 mg, no more than about 95 mg, no more than about 90 mg, nomore than about 85 mg, no more than about 80 mg, no more than about 75mg, no more than about 70 mg, no more than about 65 mg, no more thanabout 60 mg, no more than about 55 mg, no more than about 50 mg, no morethan about 45 mg, no more than about 40 mg, no more than about 35 mg, nomore than about 30 mg, no more than about 25 mg, no more than about 20mg, no more than about 15 mg or no more than about 10 mg at no more atno more than about 150 BV, no more than about 145 BV, no more than about140 BV, no more than about 135 BV, no more than about 130 BV, no morethan about 125 BV, no more than about 120 BV, no more than about 115 BV,no more than about 110 BV, no more than about 105 BV, no more than about100 BV, no more than about 95 BV, no more than about 90 BV, no more thanabout 85 BV, no more than about 80 BV, no more than about 75 BV, no morethan about 70 BV, no more than about 65 BV, no more than about 60 BV, nomore than about 55 BV, no more than about 50 BV, no more than about 45BV, or no more than about 40 BV of purge applied after a 40 g/hr butaneloading step as determined by the 2012 California Bleed Emissions Test.

In any of the aspects or embodiments described herein, the evaporativeemission control canister system has a two-day diurnal breathing loss(DBL) emissions of less than 100 mg when tested by the China 6 Type TestProcedure as described herein.

The term “fuel-side adsorbent volume” is used in reference to a volumeof adsorbent material that is proximal to the fuel vapor source, andtherefore, earlier in the fuel vapor flow path relative to a subsequentadsorbent volume, which is necessarily positioned closer to the ventport (herein, a “vent-side adsorbent volume”). As the skilled artisanwould appreciate, during a purge cycle, a vent-side or subsequentadsorbent volume(s) is contacted earlier in the purge air flow path. Forconvenience, the fuel-side adsorbent may be referred to as the “initialadsorbent volume” because it is positioned upstream in the fuel vaporflow path relative to the vent-side or subsequent adsorbent volume butthe initial adsorbent volume is not necessarily required to be the firstadsorbent volume in the canister.

FIG. 1 illustrates one embodiment of the evaporative emission controlcanister system 100 having an adsorbent volumes in-series within asingle canister. Canister system 100 includes a support screen 102, adividing wall 103, a fuel vapor inlet 104 from a fuel tank, a vent port105 opening to an atmosphere, a purge outlet 106 to an engine, thefuel-side or initial adsorbent volume 201, and vent-side or subsequentadsorbent volume 202. When an engine is off, the fuel vapor from a fueltank enters the canister system 100 through the fuel vapor inlet 104.The fuel vapor diffuses or flows into the fuel-side or initial adsorbentvolume 201, and then the vent-side or subsequent adsorbent volume 202,which together define an air and vapor flow path, before being releasedto the atmosphere through the vent port 105 of the canister system. Oncethe engine is turned on, ambient air is drawn into the canister system100 through the vent port 105. The purge air flows through volumes 202in the canister 101, and finally through the fuel-side or initialadsorbent volume 201. This purge flow desorbs the fuel vapor adsorbed onthe adsorbent volumes 201 through 202, before entering an internalcombustion engine through the purge outlet 106. In any of theembodiments of the evaporative emission control canister systemdescribed herein, the canister system may include more than onevent-side or subsequent adsorbent volume. For example, the vent-sideadsorbent volume 201 may have an additional or a plurality of vent-sideadsorbent volumes 202 before the support screen 102, as shown in FIG. 2.Additional vent-side adsorbent volumes 203 and 204 may be found on theother side of the dividing wall.

Furthermore, in still additional embodiments, the canister system mayinclude more than one type of vent-side adsorbent volume, which can beindependently selected, and/or which is comprised in one or morecontainers. For example, as shown in FIG. 3, an auxiliary chamber 300containing a vent-side adsorbent volume 301 may be in-series in terms ofair and vapor flow with the main canister 101 containing multipleadsorbent volumes. As shown in FIG. 4, the auxiliary chamber 300 maycontain two vent-side adsorbent volumes in-series 301 and 302. Theadsorbent volumes 301 and 302 may also be contained within in-serieschambers or auxiliary canisters, rather than the single chamber 300 ofFIG. 4.

In any of the embodiments described herein, the evaporative emissioncontrol system may further comprise a heating unit or a means to addheat through electrical resistance or heat conduction.

In any of the aspects or embodiments described herein, the canistersystem comprises one or more vent-side adsorbent volumes having auniform cell structure at or near the end of the fuel vapor flow path.

In certain embodiments, the at least one fuel-side or initial adsorbentvolume and the at least one vent-side or subsequent adsorbent volume (orvolumes) are in vaporous or gaseous communication and define an air andvapor flow path therethrough. The air and vapor flow path permits orfacilitates directional air or vapor flow or diffusion between therespective adsorbent volumes in the canister system. For example, theair and vapor flow path facilitates the flow or diffusion of fuel vaporfrom the at least one fuel-side or initial adsorbent volume to the atleast one vent-side or subsequent adsorbent volume (or volumes).

In any of the embodiments described herein, the at least one fuel-sideor initial adsorbent volume and the at least one vent-side or subsequentadsorbent volume(s) may be located within a single canister, separatecanisters or a combination of both. For example, in certain embodiments,the system comprises a canister comprising a fuel-side or initialadsorbent volume, and one or more vent-side or subsequent adsorbentvolumes, wherein the vent-side or subsequent adsorbent volumes areconnected to the fuel-side initial adsorbent volume such that they arein vaporous or gaseous communication forming a vapor flow path, andallowing air and/or vapor to flow or diffuse therethrough. In certainaspects, the canister permits sequential contact of the adsorbentvolumes by air or fuel vapor.

In additional embodiments, the system comprises a canister comprising aninitial adsorbent volume, and one or more subsequent adsorbent volumesconnected to one or more separate canisters comprising at least oneadditional subsequent adsorbent volume, wherein the subsequent adsorbentvolumes are connected to the initial adsorbent volume such that they arein vaporous or gaseous communication forming a vapor flow path, andallowing air and/or fuel vapor to flow or diffuse therethrough.

In certain embodiments, the system comprises a canister comprising afuel-side or an initial adsorbent volume, and one or more vent-side orsubsequent adsorbent volumes connected to one or more separate canisterscomprising at least one additional subsequent adsorbent volume, whereinthe one or more vent-side adsorbent volume and the at least oneadditional subsequent adsorbent volume are connected to the initialadsorbent volume such that they are in vaporous or gaseous communicationforming a vapor flow path, and allowing air and/or fuel vapor to flow ordiffuse therethrough, wherein at least one of the adsorbent volumes inthe system is a shaped adsorbent material as described herein having anASTM BWC of greater than 13 g/dL, and wherein the shaped adsorbentmaterial has a ratio of pore volumes of 0.05-1 micron to 0.05-100 micronas described herein, e.g., of greater than about 80%, and wherein thecanister system, when tested by BETP, has a two-day diurnal breathingloss (DBL) emissions of no more than 20 mg at 150 bed volumes of purgeapplied after the 40 g/hr butane loading step, as determined by the 2012California Bleed Emissions Test Procedure (BETP), or a DBL of no morethan 90 mg at 150 bed volumes of purge applied after the 40 g/hr butaneloading step, as determined by the 2012 BETP, or a DBL of no more than80 mg at 150 bed volumes of purge applied after the 40 g/hr butaneloading step, as determined by the 2012 BETP, or a DBL of no more than70 mg at 150 bed volumes of purge applied after the 40 g/hr butaneloading step, as determined by the 2012 BETP, or a DBL of no more than60 mg at 150 bed volumes of purge applied after the 40 g/hr butaneloading step, as determined by the 2012 BETP, or a DBL of no more than50 mg at 150 bed volumes of purge applied after the 40 g/hr butaneloading step, as determined by the 2012 BETP, including all values inbetween.

In certain embodiments, the system comprises a canister comprising afuel-side or initial adsorbent volume, and one or more vent-side orsubsequent adsorbent volumes connected to one or more separate canisterscomprising at least one additional subsequent adsorbent volume, whereinthe one or more vent-side adsorbent volume and the at least oneadditional subsequent adsorbent volume connected to the fuel-sideinitial adsorbent volume such that they are in vaporous or gaseouscommunication forming a vapor flow path, and allowing air and/or fuelvapor to flow or diffuse therethrough, wherein at least one of theadsorbent volumes in the system is a shaped adsorbent as describedherein having an ASTM BWC of greater than 13 g/dL, and wherein theshaped adsorbent material has a ratio of pore volumes of 0.05-1 micronto 0.05-100 micron as described herein, e.g., of greater than about 80%,and wherein the canister system, when tested according to a China 6 TypeTest Procedure described herein, has a two-day diurnal breathing loss(DBL) emissions of no more than 100 mg after sequential test prep of theelevated temperature soak, the elevated temperature purge, and the 20°C. soak, or a two-day diurnal breathing loss (DBL) emissions of no morethan 85 mg after sequential test prep of the elevated temperature soak,the elevated temperature purge, and the 20° C. soak, or a two-daydiurnal breathing loss (DBL) emissions of no more than 70 mg aftersequential test prep of the elevated temperature soak, the elevatedtemperature purge, and the 20° C. soak, or a two-day diurnal breathingloss (DBL) emissions of no more than 55 mg after sequential test prep ofthe elevated temperature soak, the elevated temperature purge, and the20° C. soak, or a two-day diurnal breathing loss (DBL) emissions of nomore than 40 mg after sequential test prep of the elevated temperaturesoak, the elevated temperature purge, and the 20° C. soak, including allvalues in between.

In any of the aspects or embodiments described herein, the fuel-side orinitial adsorbent volume is the first and/or second adsorbent volume, assuch, the vent-side or subsequent adsorbent volumes are those downstreamin the fluid flow path towards the vent port whether in the same or aseparate canister or both.

In any aspects or embodiments described herein, the canister systemcomprises at least one vent-side adsorbent volume having at least oneof: (i) an incremental adsorption capacity at 25° C. of from 1 gramn-butane/L to less than 35 grams n-butane/L between vapor concentrationsof 5 vol % and 50 vol % n-butane, (ii) an effective BWC of less than 3g/dL, (iii) a g-total BWC of less than 6 grams, or (iv) a combinationthereof. In certain embodiments, the canister comprises at least oneventi-side adsorbent volume having an incremental adsorption capacity at25° C. of about 35, about 34, about 33, about 32, about 31, about 30,about 29, about 28, about 37, about 36, about 35, about 34 about 23,about 22, about 21, about 20, about 19, about 18, about 17, about 16,about 15, about 14, about 13, about 12, about 11, about 10, about 9,about 8, about 7, about 6, about 5, about 4, about 3, about 2, or about1 g/L between vapor concentrations of 5 vol % and 50 vol % n-butane

In any of the aspects or embodiments described herein, the canistersystem comprises at least one fuel-side adsorbent volume having anincremental adsorption capacity at 25° C. of greater than about 35 gramsn-butane per liter (g/L) to about 90 g/L between vapor concentration of5 vol % and 50 vol % n-butane, or about 36, about 37, about 38, about39, about 40, about 41, about 42, about 43, about 44, about 45, about46, about 47, about 48, about 49, about 50, about 51, about 52, about53, about 54, about 55, about 60, about 65, about 70, about 75, about80, about 85, about 90 or more grams n-butane per liter (g/L) betweenvapor concentration of 5 vol % and 50 vol % n-butane. In any of theaspects or embodiments described herein, the canister system comprisesat least one fuel-side adsorbent volume having an incremental adsorptioncapacity at 25° C. of greater than about 35, 40, 45, 50, 55, 60, 65, 70,75, 80, 85, 90 or more grams n-butane per liter (g/L) to about 90 g/Lbetween vapor concentration of 5 vol % and 50 vol % n-butane.

In any aspects or embodiments described herein, the canister systemcomprises at least one vent-side adsorbent volume having an incrementaladsorption capacity at 25° C. of less than about 35 grams n-butane perliter (g/L) between vapor concentration of 5 vol % and 50 vol %n-butane, or about 34, about 33, about 32, about 31, about 30, about 19,about 18, about 17, about 16, about 15, about 14, about 13, about 12,about 11, about 10, about 9, about 8, about 7, about 6, about 5, about4, about 3, about 2, or about 1 grams n-butane per liter (g/L) betweenvapor concentration of 5 vol % and 50 vol % n-butane.

EXAMPLES

Table 1 has the descriptions and properties of comparative commercialexamples 1 through 8. Commercial examples of shape & activate activatedcarbon adsorbents include CNR 115 (Cabot Corporation, Boston, Mass.),KMAZ2 and KMAZ3 (Fujian Xinsen Carbon, Fujian Sheng, China), 3GX(Kuraray Chemical Ltd., Bizen-shi, Japan), and NUCHAR® BAX 1100 LD, BAX1500, BAX 1500E, BAX 1700 (Ingevity Corporation, North Charleston,S.C.). All these adsorbents are in the form of cylindrical pellets ofabout 2-2.5 mm in diameter. Table 2 has the descriptions and propertiesof inventive grind & bind examples.

Examples 9 and 10 were prepared from carbon powder made from phosphoricacid-activated sawdust (NUCHAR® FP-1100 by Ingevity Corporation). Thiscarbon powder had a powder butane activity of 42.6 g/100 g, and a meanparticle diameter of 39 microns, a d_(10%) of 8 microns, d_(50%) of 35microns, and a d_(90%) of 78 microns, as measured by a MalvernPanalytical model Mastersizer 2000 laser particle size analyzer. In thepreparation of CMC-bound Example 9 carbon pellets, the dry ingredientformulation was 95.3 wt % carbon powder and 4.7 wt % CMC. For mixing andconditioning the dry mix in preparation for extrusion, a Simpson modelLG mix muller (Simpson Technologies Corporation, Aurora, Ill.), whereshear mixing/kneading was conducted for 35-50 minutes, with aliquots ofwater added for gaining the needed plasticity for extrusion. An augerextruder (The Bonnot Company, Akron, Ohio), equipped with a die platewith 2.18 mm diameter holes and a cutter blade, was used for shapinginto pellets. The resulting pellets were tumbled for 4 minutes in abatch rotary pan pelletizer, dried as a static bed in a tray oven at110° C. for about 16 hrs, and then cured as a static bed in recirculatedair for 3 hrs at 150° C. In the preparation of example 10, the sameprocess as for example 9 was used except for the followingdifferences: 1) Instead of CMC binder, bentonite clay binder (NATIONAL®STANDARD SPCL GRIND grade from Bentonite Performance Minerals LLC) wasused in a dry ingredient formulation of 81 wt % carbon and 19% clay, and2) Instead of curing, the resulting dried pellets were calcined at 650°C. for 30 minutes in nitrogen flow in a fluidized bed in a verticalquartz tube furnace.

Example 12 was prepared the same as example 9, except that there was nocuring step after tray oven drying, and the sawdust-based phosphoricacid-activated carbon powder ingredient (INGEVITY CORPORATION) hadhigher powder butane activity of 56.2 g/100 g, and the followingparticle size properties: A mean particle diameter of 40 microns, ad_(10%) of 4. microns, d_(50%) of 31 microns, and a d_(90%) of 88microns.

Examples 11, 13, 14, and 16 were prepared with CMC binder by thefollowing process. The activated carbon powder ingredients werephosphoric acid-activated sawdust (INGEVITY CORPORATION) of variedbutane activity properties. The butane activities of the carbon powderswere 59.4, 61.4, 59.8, and 64.9 g/100 g for examples 11, 13, 14, and 16,respectively. The powders had a mean particle diameter of about 40microns, a d_(10%) of about 10 microns, d_(50%) of about 40 microns, anda d_(90%) of about 80 microns. In preparing the pellets, the carbonpowder and CMC binder powder (95.3 wt % carbon powder and 4.7 wt % CMC)were blended in a plow mixer for about 20-30 minutes, with aliquots ofwater added for gaining the needed plasticity for extrusion. Theresulting blend was processed through two successive single screwextruders with the second extruder equipped with a die plate with 2.18mm diameter holes and a cutter blade for shaping the blend into pellets.The resulting pellets were tumbled for about 4 minutes in a continuousrotary tumbler, dried and then cured to about 130° C. in a moving bedwith recirculated air for about 40 minutes.

Example 15 was prepared by the same clay-bound method as example 10,except that the ingredient activated carbon powder was made fromcomparative example 6 pellets (NUCHAR® BAX 1500) by preparing the powderactivated carbon ingredient by grinding the example 6 pellets in ahammer mill (model WA-6-L SS by Buffalo Hammer Mill Corp., Buffalo,N.Y.) equipped with a 0.065″ Φ opening screen. The resulting carbonpowder used in making the example 15 pellets had the followingproperties: Powder butane activity of 62.2 g/100 g, and a mean particlediameter of 39 microns, a d_(10%) of 4 microns, d_(50%) of 28 microns,and a d_(90%) of 88 microns.

While the examples 9-16 were prepared with phosphoric acid activatedcarbons, the effects and benefits described herein would be obtained bybinding and shaping activated carbon powder ingredient made from anycarbonaceous raw material (e.g., wood, wood dust, wood flour, cottonlinters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch,petroleum coke, coal tar pitch, fruit pits, fruit stones, nut shells,nut pits, sawdust, etc.) and that had its porosity generated by otherchemical or thermal activation processes as long as there issufficiently high butane activity in the carbon powder for attainingsufficiently high ASTM BWC of the final shaped adsorbent. As known inthe art, within the <5 nm size pore volume that contributes to thecondensed n-butane phase in the adsorbent (i.e., butane activity by theASTM 5228 method), a preference is to have the pore distributionpredominantly of the small mesopore size of 1.8-5 nm. FIG. 18 shows agood correlation between the butane activity of the activated carbonpowder ingredients and the resulting ASTM BWC of the finished boundpellet for examples 9 through 16. The trend shows, for example, thatactivated carbon powder with a butane activity greater than 50 g/100 gis needed for a pellet with greater than 13 g/dL ASTM BWC.

FIG. 5 shows 2^(nd) day DBL emissions data by the BETP test protocol fora variety of commercial carbons of a range of ASTM BWC properties,examples 1 through 8, as tested as the volume fill in the DefinedCanister system as described herein (i.e., a 2.1 L canister system—1.4 Land 0.7 L volume fills as volumes 201 and 202, respectively, of FIG. 1).The relationship shown is the state of the art for the effects ofworking capacity on DBL emissions, that is, a sharp increase in DBLemissions as BWC is increased beyond 12 g/dL BWC, to above 14 g/dL BWC.These high BWC examples include NUCHAR® BAX 1500, BAX 1500E, BAX 1700(Ingevity Corporation); 3GX (Kuraray Chemical Ltd.), and KMAZ3 (FujianXinsen Carbon, Fujian Sheng, China); all prepared by shape & activatemethods. As described in U.S. RE 38,844 (“US '844”), higher bleedemissions for higher BWC volume fills in a FIG. 1 canister system are tobe expected as an inevitable result of the equilibrium adsorptionproperties of the adsorbent, specifically the isotherm slope and thedesign of the canister system with an elongated vapor flow path throughthe adsorbent volumes in-series. It is a dynamic where, during purge,high working capacity adsorbent towards the vent-side of the canistersystem, as a result of its great amount of desorbed vapors, contaminatesthe downstream purge flow within the canister system along the vaporflow path, thus progressively interfering with the concentrationdifference driving force of the purge towards the fuel vapor source.This depleted concentration driving force for desorption leaves agreater retained heel towards the fuel-source and creates the heeldistribution conditions across the canister system. The heeldistribution then leads to greater amounts of subsequent vapor diffusionand vapor contamination back towards the vent-side during the diurnalsoak, causing a high level of emissions during the diurnal breathingevent. This is the dilemma of high DBL emissions as a knowncharacteristic high BWC adsorbents, which has appeared to be anunavoidable problem, only be addressed through the added costs, systemsize, and complexities of the approaches described above.

In FIG. 5, examples based on the disclosure in US '844 were testedincluding a 16.0 g/dL BWC pellet fill of a similar 2.1 L canister system(●). For these examples, the high BWC adsorbent in a 0.3 L vent-sidevolume is replaced by an adsorbent with lower ASTM BWC properties (e.g.,FIG. 4 where volumes 201 and 202 are a single 1.5 L volume of 16.0 g/dLBWC carbon pellets, where volume 203 is a 0.3 L volume of 16.0 g/dL BWCcarbon pellets, and where the 0.3 L vent-side volume 204 has the 16.0g/dL BWC carbon pellets alternatively replaced by 5.0, 5.7, or 11.9 g/dLBWC adsorbent pellets). The cited BWC values for the x-axis correspondwith the ASTM BWC of the 204 vent-side volume pellets. The activatedcarbon honeycomb example of US '844 with 4.0 g/dL BWC is also shown (▪),which is a system similar to FIG. 3, consisting of the 2.1 L dualchamber canister with the 16.0 g/dL BWC pellets in volumes 201 through204 and the carbon honeycomb contained in an auxiliary canister 300 asadsorbent fill 301. This data set from US '844 follows the same datatrend of the commercial products in FIG. 5. Therefore, in effect in FIG.5, the canister systems in US '844 with a majority content of high BWCadsorbent have the same DBL emissions as the system otherwise solelyfilled with the lower BWC adsorbent, albeit by the complication ofreplacing a portion of the high working capacity adsorbents in the main2.1 L canister system with an alternative grade substitute adsorbent orby installing an added auxiliary chamber containing additionaladsorbent.

It is significant in FIG. 5 that the comparative grind & bind 2.1 Lvolume fill example, the comparative shape & activate 2.1 L volume fillexample, and the US '844 grind & bind vent-side replacement example, allin the 11-12 g/dL BWC range, show no effect from the method ofpreparation on the 2^(nd) day DBL emissions, which all fall within arange of about 70-90 mg. As such, the trade-off for a given maincanister design is DBL emissions levels for a single type of adsorbentfill that is dependent on its level of working capacity, or an addedcomplexity of adsorbent fill through multiple types of adsorbents insuccessive chambers, or in added chambers in-series.

In contrast with the comparative examples 1 through 8 in FIG. 5,examples 11 through 16 were prepared with substantially lower DBLemissions by the BETP test protocol than expected for their ASTM BWCproperties of 13.7-14.7 g/dL (see FIG. 6). The DBL emissions of theexamples are at a fraction of the expected amounts, e.g., 50-90 mgcompared with 150-229 mg for commercial examples at comparably high BWC.The trend has 13 g/dL ASTM BWC for the inventive adsorbent at less thanhalf the DBL emissions expected for its working capacity (60 mg vs.about 130 mg).

Two important, highlighted examples are 6 and 15. Example 15 wasprepared from the comparative example 6 by the steps of grinding the BAX1500 pellets, combining the activated carbon powder with bentonite clayand water, and shaping, drying, and, lastly, calcining in an oxygen-freeatmosphere. The resulting 2 mm pellets of example 15 have a BWC of 14.6g/dL, but the Day 2 DBL emissions are slightly lower than the 11.2 g/dLBWC pellets of Example 1.

One common feature for examples 11 through 16 with 13+ g/dL ASTM BWC isthat they are prepared by “grind & bind” processing, that is combiningactivated carbon powder with a binder, either organic or inorganic, andforming a shaped adsorbent material as described herein. While not to belimited by theory, the potential causes for the unexpected and extremelyuseful DBL emissions performance advantage at these high ASTM BWCproperties, above 13 g/dL, include the presence of a uniformdistribution of adsorptive pores across the adsorbent its interior andthe presence of a uniform internal network of pores between the powderparticles for vapor transport. All conventional high working capacityproducts (e.g., 13+ g/dL ASTM BWC), for maximizing working capacity andminimizing the number of unit operations, are made by processes thatinvolve shaping a carbonaceous or carbon-containing ingredient into apellet, and then activating to form the adsorptive porosity. As shown,herein, the high BWC grind & bind adsorbents because of their surprisingadvantage of moderated DBL emissions have a multitude of end-useadvantages for canister system design that overcome the added processingsteps and despite some trade-off in ultimate working capacity potential.As a result of bonding rigid powder particles that are alreadyactivated, the grind & bind 13+ g/dL ASTM BWC adsorbents havedistinctively narrow and smaller pore size or volume distributions inthe macropore size range of 0.05 to 100 microns, as compared with thebroader distributions, balanced between small and large size macropores,as present in conventional high BWC shape & activate adsorbents.

The surprising result of combined high working capacity with low DBLemissions for the shaped adsorbent materials as described herein isparticularly unexpected because conventional high working capacityadsorbents of over 13 g/dL ASTM BWC that are exclusively made byconventional shape & activate thermal or chemical activation processeshave pore volumes in the total macropore size range of 0.05-100 micronsthat are balanced between smaller size macropores 0.05-0.5 microns insize and larger size macropores 0.5-100 micron in size. Such a pore sizedistribution is taught to be favorably important for desorption andbleed emission performance for evaporative emission control adsorbentsdesigned for higher gasoline vapor working capacity, for example withincremental adsorption capacities between 5-50% n-butane of greater than35 g/L, which correlates to greater than about 8 g/dL ASTM BWC. See U.S.Pat. No. 9,322,368, with examples provided at about 50% of the totalmacropore volume in pores of 0.05-0.5 micron size, as opposed to anunfavorable comparative example with about 90% of the total macroporevolume in pores of 0.05-0.5 micron size.

For commercial adsorbents in the 11-12 g/dL ASTM BWC range where thepellets are prepared by the grind & bind method (comparative example 1)or the shape & activate (comparative examples 2 and 3) method, themacropore size distributions vary widely, from over 90% of pore volumesmaller than 1 micron, to less than 10% smaller than 1 micron (see FIG.7), with little to indicate a large potential benefit in DBL emissionsfor high BWC adsorbents of 13+g/dL. Two experimental grind & bindsamples made with CMC or clay binder and the same powder activatedcarbon were prepared near this 11-12 g/dL BWC range (examples 9 and 10).As shown in FIG. 8, the differences in DBL emissions performance are notvery great among the samples despite the differences in macroporedistributions expressed as the function of the percentage volumes0.05-0.5 microns. A better correlation is shown for percentage volumes0.05-1 micron (FIG. 8). As might be expected from U.S. Pat. No.9,322,368 (“U.S. '368”), there is an improvement in DBL emissions as themacropore distribution of the comparative commercial examples isoptimized towards about 50% in 0.05-0.5 micron size pores, however, thedifference is only about 40 mg between examples made by the two methods.The example 9 with its percentage of near 90% of macropore pore volumein the 0.05-0.5 micron size has the lowest DBL emissions of the groupwhich is surprising given its pore size distribution skewed to smallsize macropores which were previously taught to be avoided.

In contrast, as a consequence of maximizing working capacity bypreparing the adsorbent activated carbon by shape & activate processes,perhaps due to the use of natural lignocellulosic ingredients, shapingplastic char particles, and employing activatable binders (i.e., incontrast with compacting rigid, already activated carbon powderparticles with diluent binder additive), all conventional commercialactivated carbons with ASTM BWCs above 13 g/dL have a broad sizedistribution of macropores, as shown in FIG. 10. These comparativeexamples 4 through 8 have only about 20-60% of total macropore volume inpores 0.05-0.5 micron in size and only about 40-70% 0.05-1 micron insize, which is consistent with a preferred macropore size distributiontaught by U.S. Pat. No. 9,322,368 of about 50% of total macropore volumein pores 0.05-0.5 micron in size. The inventive grind & bind exampleswith ASTM BWC above 13 g/dL with substantially lower DBL emissions havemacropore distributions skewed heavily to small macropores, away fromthe taught target and towards the smaller size distribution to beavoided (FIG. 11). For these examples 11 through 16, the proportion oftotal macropores that are 0.05-0.5 microns in size is 58-92% (FIG. 12)and the proportion of total macropores that are 0.05-1 micron in size is90%, or more (FIG. 13). As with the examples 9 and 10 at 12.0-12.6 g/dLASTM BWC and the comparative examples 11-12 g/dL ASTM BWC in FIG. 9, thecomparative examples and grind & bind examples 11-16 at 13+ g/dL BWCshow a good correlation of bleed emissions with the percent of totalmacropore volume in pores 0.05-1 micron in size, however, the effect issurprisingly stronger for the higher BWC materials (see FIG. 13). Forexample, comparative example 6 has about half of its total macroporevolume in pores 0.05-1 microns and its bleed emission were reduced byabout 100 mg by reconstituting this pellet formed by a shape & activateprocess into the grind & bind pellet of Example 15 which has 90% of itsmacropores in that size range.

In attempting to understand the unexpected low DBL emission result ofgrind & bind as compared with shape & activate at the high BWC, a closestudy was conducted of the total macropore volume on both a cc/g and acc/cc-particle basis, of the g/dL butane retentivity from the ASTM BWCtest, and of the ratio of the total macropore volume to the pore volumein the adsorptive pore size range (i.e., ratio of the volume 0.1-100micron in size to the volume<0.1 micron, the “M/m” ratio in U.S. Pat.No. 9,174,195, or “US '195”). This analysis further showed the low DBLemission result to be unexpected. For example, FIGS. 14 and 15 show thatthe total macropore volume is not a predictor of DBL emissionsperformance. The 13+ g/dL BWC grind & bind examples 11 through 16 withlow emissions have the same range of total macropore volume on both acc/g-carbon basis and a cc/cc-particle basis as the comparative examples4 through 8 with high DBL emissions also of 13+ g/dL ASTM BWC but madeby shape & activate processes. In US '195, the ratio of total macroporevolume 0.1-100 micron in size to “micropore” volume<0.1 micron in sizeis taught as optimized within a range of 65-150% for an adsorbent to beused near the atmospheric port. However, as shown in FIG. 16, the M/mproperties of the low DBL emission grind & bind examples are the same asthose of the comparative examples. The low DBL emissions obtained wereoutside of the 65-150% M/m range taught by U.S. Pat. No. 9,174,195.Notably and as highlighted in FIG. 16, the low DBL emission grind & bindexample 15 was actually farther from the optimum M/m range compared withits precursor carbon, comparative example 6. Additionally, a maximumretentivity target of 1.7 g/dL is cited US '195 for an adsorbent to beused near the atmospheric port. However, as shown in FIG. 17, grind &bind examples 9 through 16 and comparative examples 1 through 8 have asimilar range of retentivities of about 2-3 g/dL. Notably and ashighlighted in FIG. 17, the low DBL emission grind & bind example 15actually has higher retentivity compared with its precursor carbon,comparative example 6.

Such a lower DBL emission performance characteristic while providinghigh working capacity is of great benefit to the designers ofevaporative emission control canisters, as one skilled in the art wouldunderstand, for allowing the use of less costly, smaller size, and lesscomplex approaches for meeting emissions requirements while stillproviding high working capacity for vapor recovery, especially in theface of the challenges imposed by the aforementioned advances inpowertrains and air/fuel mixture and flow rate management (e.g., hybrid,HEV, turbocharged engines, turbo-assisted engines, and GDI engines) andin the face of ever stricter fuel vapor emission regulations. Forexample, one embodiment is to simplify a canister system, such as inU.S. Pat. No. 9,732,649, where the presently described shaped adsorbentmaterials replaces the 1800 cc of BAX 1500 in the main canister type #1(similar to the volume fill locations of 201, 202, and 203 in FIG. 4),generating less of a DBL emission challenge for the multiple auxiliarychambers and thereby providing target emissions performance for thesystem with fewer such auxiliary chambers (e.g., eliminating adsorbent301 or 302 n auxiliary chamber 300 in FIG. 4). Another embodiment, suchas in U.S. Pat. No. 9,732,649, would alternatively simplify the maincanister fill of main canister type #1 by the use of 2100 cc of the highworking capacity inventive adsorbent as the sole adsorbent in the maincanister chambers, eliminating the production complexity of filling thecanister with multiple types of adsorbents and eliminating the expenseof high cost low working capacity bleed emission pellets in the 300 ccon the vent-side of that example system (e.g., have volumes 201 and 202in FIG. 1 filled with the one inventive adsorbent, rather than volumes201-203 in FIG. 3 with a conventional high working capacity adsorbent incombination with volume 204 containing low working capacity, low bleedemission pellets). In certain canister system embodiments containing thepresently described shaped adsorbent materials, the target of less than20 mg day 2 DBL emissions is met when tested with less than 210 liters,or with less than 100 bed volumes, purge applied after the 40 g/hrbutane loading step, as determined by the 2012 California BleedEmissions Test Procedure (BETP).

Another embodiment uses the high working capacity presently describedshaped adsorbent material pellets in an auxiliary canister, as taught inU.S. Pat. No. 9,657,691 as a replacement for the conventional 13+ g/dLBWC pellets (e.g., similar to the adsorbent fill 301 in auxiliarycanister 300 in FIG. 4). By doing so for the system shown in U.S. Pat.No. 9,657,691, the need for the heating of a subsequent volume of lower6-10 g/dL BWC adsorbent (e.g., volume 302 in FIG. 4) may be eliminated,or the subsequent adsorbent may be eliminated entirely.

TABLE 1 Example Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 PelletGrind Shape Shape Shape Shape Shape Shape Shape Preparation & Bind & Act& Act & Act & Act & Act & Act & Act Method Product BAX CNR KMAZ2 3GX BAXBAX KMAZ3 BAX Grade 1100 LD 115 1500E 1500 1700 PV <1.8 nm, cc/g 0.1570.327 0.225 0.011 0.178 0.289 0.313 0.241 PV 1.8-5 nm, cc/g 0.625 0.4710.632 0.968 0.996 0.967 0.969 1.157 PV 5-50 nm, cc/g 0.342 0.045 0.2510.060 0.307 0.253 0.272 0.168 PV 0.05-1 0.468 0.029 0.156 0.197 0.3590.250 0.190 0.170 micron, cc/g PV 1-100 0.051 0.456 0.257 0.342 0.1670.213 0.220 0.197 micron, cc/g Particle Density 0.553 0.586 0.533 0.5160.431 0.499 0.448 0.442 <100 micron, cc/g PV <1.8 nm, 0.087 0.192 0.1200.006 0.077 0.144 0.140 0.107 cc/cc PV 1.8-5 nm, 0.346 0.276 0.337 0.5000.429 0.483 0.434 0.511 cc/cc PV 5-50 nm, 0.189 0.026 0.134 0.031 0.1320.126 0.122 0.074 cc/cc PV 0.05-1 0.259 0.017 0.083 0.102 0.155 0.1250.085 0.075 micron, cc/cc PV 1-100 0.028 0.267 0.137 0.176 0.072 0.1060.098 0.087 micron, cc/cc PV <0.1 micron, 1.14 0.86 1.13 1.05 1.52 1.541.59 1.58 cc/g PV 0.1-100 0.456 0.473 0.350 0.507 0.361 0.353 0.3240.300 micron, cc/g PV 0.05-100 0.519 0.486 0.412 0.539 0.526 0.463 0.4100.367 micron, cc/g PV 0.05-100 0.287 0.285 0.220 0.278 0.227 0.231 0.1840.162 micron, cc/cc PV % 0.05-1 90%  6% 38% 37% 68% 54% 46% 46%micron/0.05- 100 micron PV % 0.05-0.5 59%  5% 31% 19% 60% 43% 40% 35%micron/0.05- 100 micron, “M/M” PV % 0.1-100 40% 55% 31% 48% 24% 23% 20%19% micron/<0.1 micron, “M/m” Apparent 0.319 0.367 0.341 0.332 0.3000.285 0.299 0.290 Density, g/cc Butane Activity, 40.1 38.6 41.9 50.257.7 62.0 63.9 68.3 g/100 g ASTM BWC, 11.23 11.77 11.84 14.08 14.4015.58 16.12 17.05 g/dL Butane Purge 0.877 0.830 0.829 0.844 0.830 0.8830.844 0.860 Ratio Retentivity, g/dL 1.59 2.40 2.43 2.59 2.91 2.09 2.982.76 Fuel Tank Size 15 15 15 20 20 20 20 20 for DBL Test, gal TankUllage, gal 11.0 11.0 11.0 12.8 12.8 12.8 12.8 14.4 Day 1 Load, g 24.829.6 27.3 33.1 31.3 32.7 36.0 36.2 Day 2 Load, g 25.8 28.0 25.4 30.928.8 32.5 35.5 35.4 Day 2 DBL 66 107 94 220 152 158 223 224 Emissions,mg

TABLE 2 Example Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16Pellet Grind Grind Grind Grind Grind Grind Grind Grind Preparation &Bind & Bind & Bind & Bind & Bind & Bind & Bind & Bind Method PV <1.8 nm,cc/g 0.163 0.150 0.161 0.276 0.178 0.272 0.163 0.300 PV 1.8-5 nm, cc/g0.760 0.663 0.789 0.759 0.792 0.799 0.760 0.819 PV 5-50 nm, cc/g 0.1600.292 0.207 0.141 0.210 0.156 0.160 0.136 PV 0.05-1 0.418 0.254 0.4760.438 0.459 0.430 0.247 0.429 micron, cc/g PV 1-100 0.033 0.024 0.0270.027 0.027 0.032 0.028 0.033 micron, cc/g Particle Density 0.518 0.5960.511 0.486 0.478 0.500 0.574 0.521 <100 micron, cc/g PV <1.8 nm, 0.0840.089 0.082 0.134 0.085 0.136 0.093 0.156 cc/cc PV 1.8-5 nm, 0.394 0.3950.403 0.369 0.378 0.400 0.436 0.427 cc/cc PV 5-50 nm, 0.083 0.174 0.1060.069 0.100 0.078 0.092 0.071 cc/cc PV 0.05-1 0.217 0.151 0.243 0.2130.219 0.215 0.142 0.224 micron, cc/cc PV 1-100 0.017 0.014 0.014 0.0130.013 0.016 0.016 0.017 micron, cc/cc PV <0.1 micron, 1.09 1.12 1.201.19 1.22 1.24 1.09 1.27 cc/g PV 0.1-100 0.377 0.247 0.425 0.400 0.4090.400 0.238 0.396 micron, cc/g PV 0.05-100 0.451 0.277 0.502 0.465 0.4860.461 0.275 0.463 micron, cc/g PV 0.05-100 0.234 0.165 0.256 0.226 0.2320.231 0.158 0.241 micron, cc/cc PV % 0.05-1 93% 91% 95% 94% 94% 93% 90%93% micron/0.05- 100 micron PV % 0.05-0.5 86% 38% 76% 63% 92% 64% 58%85% micron/0.05- 100 micron, “M/M” PV % 0.1-100 35% 22% 35% 34% 33% 32%22% 31% micron/<0.1 micron, “M/m” Apparent 0.340 0.380 0.319 0.325 0.3220.324 0.366 0.320 Density, g/cc Butane Activity, 41.8 36.5 49.5 50.250.4 51.2 46.4 54.6 g/100 g ASTM BWC, 12.60 11.97 13.75 13.91 13.9113.97 14.60 14.67 g/dL Butane Purge 0.884 0.861 0.872 0.854 0.857 0.8420.860 0.840 Ratio Retentivity, g/dL 1.62 1.92 2.03 2.39 2.32 2.62 2.392.80 Fuel Tank Size 15 15 20 20 20 20 20 20 for DBL Test, gal TankUllage, gal 11.0 11.0 12.8 12.8 12.8 12.8 12.8 12.8 Day 1 Load, g 24.124.9 32.6 34.0 33.4 33.8 31.1 37.0 Day 2 Load, g 23.6 24.8 31.5 33.131.8 30.6 28.8 34.0 Day 2 DBL 47 53 50 81 62 59 87 64 Emissions, mg

Determination of Apparent Density, BWC, and Powder Butane Activity

The standard method ASTM D 2854 (hereinafter “the Standard Method”) maybe used to determine the nominal volume apparent density of particulateadsorbents, such as granular and pelletized adsorbents of the size andshape typically used for evaporative emission control for fuel systems.

The standard method ASTM D5228 may be used to determine the nominalvolume butane working capacity (BWC) of the adsorbent volumes containingparticulate granular and/or pelletized adsorbents. The butaneretentivity is calculated as the difference, in units of g/dL, betweenthe volumetric butane activity (i.e., the g/cc apparent densitymultiplied by the g/100 g butane activity) and the g/dL BWC.

For powdered activated carbon ingredients for extrusion, a powder butaneactivity (“pBACT”) may be measured by number of ways that one skilled inthe art would recognize as equivalent for ascertaining that value, i.e.,the equilibrated gram weight capacity of the oven dried powder samplewhen exposed to 1.00 atm partial pressure of n-butane, for the samplethermostatted at 25° C. One suitable alternative for pBACT, for example,is based on the ASTM 5228 method, where the weight pick-up is measuredfor a smaller-than-normal amount of dried sample (0.50-1.00 g) in orderto allow unimpeded flow of n-butane gas through the sample holder tubeduring the saturation step. By this method, as was used for Examples 9through 16, a plug of glass wool is used for retaining the powderactivated carbon sample in the sample tube. In determining the weightpick-up of n-butane by the sample from adsorption, a weight correctionis applied (i.e., subtracted from the total sample holder weight gainfrom the butane saturation step) in order to account for thecontribution to the total weight gain of the sample holder tube due tothe difference in density of air in the holder initially in the gasphase, and thereby more accurately define the weight gain of n-butane bythe carbon sample due to adsorption. (Normally, this air displacementcorrection for the butane activity measurement for the 16.7 mL granularor pellet adsorbent volume in the sample holder tube is not appliedaccording to ASTM 5228, perhaps because the adsorbed weight of butane isvery large relative to the potential air displacement correction.However, the small sample size required for the testing of a smallamount of adsorbent powder in the flow apparatus requires that the airdisplacement be taken to account for accurately determining theadsorption capacity of the powder.) The gas phase butane displacementweight correction is made with the Ideal Gas Law (PV=nRT) forcalculating the weight difference for that volume filled with airinitially versus filled with n-butane gas upon saturation. The pressure,P, is 1 atm, the volume, V, is the empty sample holder volume in cc asdetermined separately by a method such as water fill, the temperature Tis the 298 K, and R is the gas constant (82.06 cc atm/K gmole). Thevalue of the number of gas phase gmoles, n, is calculated for the sampletube (neglecting the de minimis correction to the empty tube volume fromthe skeletal volume of the adsorbent sample and the volume of condensedbutane adsorbate in the adsorbent porosity). The weight correction isthe difference in mass between air (28.8 g/gmole) versus the heaviern-butane (58.1 g/gmole) for that Ideal Gas Law-calculated gmole value.

Determination of Diurnal Breathing Loss (DBL) Emissions According to aBETP Test

The evaporative emission control systems in the examples were tested bya protocol that include the following. The defined 2.1 L canister(herein and in the claims a, “Defined Canister”) that is used forgenerating the data in FIGS. 5 and 6 has, as shown in FIG. 1, a 1.4 Ladsorbent volume 201 with about a 19.5 cm height above the supportscreen 102 (e.g., ‘h’), plus a 0.7 L adsorbent volume 202 with about a19.5 cm height above the support screen 102. The 1.4 L adsorbent volume201 has an average width of 9.0 cm from the dividing wall 103 to theside wall of the canister (e.g., ‘w’), and the 0.7 L adsorbent volume202 has an average width of 4.5 cm from the dividing wall 103 to itssidewall. Both adsorbent volumes 201 and 202 have a similar depth (intothe page in FIG. 1) of 8.0 cm.

Each example adsorbent fill was uniformly preconditioned (aged) byrepetitive cycling of gasoline vapor adsorption using certified Tier 3fuel (8.7-9.0 RVP, 10 vol % ethanol) and 300 nominal bed volumes of dryair purge at 22.7 LPM based on the main canister (e.g., 630 liters for a2.1 L main canister). (The U.S. RE38,844 work was conducted withcertified TF-1 fuel.) The gasoline vapor load rate was 40 g/hr and thehydrocarbon composition was 50 vol %, generated by heating two liters ofgasoline to about 38° C. and bubbling air through at 200 ml/min. Thetwo-liter aliquot of fuel was replaced automatically with fresh gasolineevery 1 hr 55 min until 5000 ppm breakthrough as butane was detected byan FID (flame ionization detector) or infrared detector. A minimum of 25aging cycles were used on a virgin canister. The gasoline workingcapacity (GWC) may be measured as the average weight loss of purgedvapors for the last 2-3 cycles and is reported as grams per liter ofadsorbent volumes in the canister system. In proceeding further tomeasure bleed emission performance, the GWC aging cycles were followedby a single butane adsorption/air purge step. This step was to loadbutane at 40 g/hour at a 50 vol % concentration in air at one atm to5000 ppm breakthrough, soak for one hour, then purge with dry air for 21minutes with a total purge volume attained by selecting the appropriateconstant air purge rate for that period. The canister was then soakedwith the ports sealed for about 18-20 hrs at about 25° C. (where 24 hrsis the midpoint of the requirement for the soak time). For the DBL datain FIGS. 5-6, 8-9, and 12-17, the total purge volume following the abovesingle butane adsorption loading was 315 L, equivalent to 150 BV for the2.1 L adsorbent fill of the defined canister.

The DBL emissions were subsequently generated by attaching the tank portof the example to a fuel tank filled with CARB LEV III fuel (6.9-7.2RVP, 10% ethanol). (The U.S. RE38,844 work was conducted CARB Phase IIfuel.)

It is notable that, in order to appropriately challenge canister systemsfor the size fuel tank for which their working capacity would beleveraged in practice (i.e., by providing a more realistic diurnal vaporload, and thereby generating appropriately comparable emissions data),smaller fuel tanks with smaller ullage were employed for the canistersystems containing the examples with <12.6 g/dL ASTM BWC. That is, thecanister systems with 13+ g/dL ASTM BWC had appropriately greaterloading challenges during the diurnal test for emissions control becauseof the larger size tanks and larger size ullage to which they wereconnected, i.e., for a given ASTM BWC fill, an otherwise undersized tanksystem would be underchallenged. In detail, the <12.6 g/dL ASTM BWCcanister system examples were connected to a 15 gallon tank filled with4 gallons of liquid fuel (11.0 gal ullage). The 13.7-16.1 g/dL ASTM BWCcanister system examples were connected to a 20 gallon tank filled with7.2 gallons of liquid fuel (12.8 gal ullage). The 17.1 g/dL ASTM BWCcanister system example was connected to a 20 gallon tank filled with5.6 gallons of liquid fuel (14.4 gal ullage), thereby providing thelarger ullage space needed for this extremely high ASTM BWC canisterfill, but with an existing 20 gallon-size tank.

Prior to attachment, the filled fuel tank had been stabilized at 18.3°C. for 18-20 hours while venting (where 24 hrs is the midpoint of therequirement of the soak time while venting). The tank and the canistersystem were then temperature-cycled per CARB's two-day temperatureprofile, each day from 18.3° C. to 40.6° C. over 11 hours, then backdown to 18.3° C. over 13 hours. Emission samples were collected from theexample vent at 6 hours and 12 hours during the heat-up stage into Kynarbags (The U.S. RE38,844 work had sample collection at 5.5 and 11 hours).The Kynar bags were filled with nitrogen to a known total volume basedon pressure and then evacuated into a FID to determine hydrocarbonconcentration. The FID was calibrated with a precisely known-butanestandard of about 5000 ppm concentration. From the Kynar bag volume, theemissions concentration, and assuming an ideal gas, the mass ofemissions (as butane) was calculated. For each day, the mass ofemissions from the two readings were added. Following CARB's protocolthe day with the highest total emissions was reported as “2-dayemissions.” In all cases, the highest emissions were on Day 2. Thisprocedure is generally described in SAE Technical Paper 2001-01-0733,titled “Impact and Control of Canister Bleed Emissions,” by R. S.Williams and C. R. Clontz, and in CARB's LEV III BETP procedure (sectionD.12 in California Evaporative Emissions Standards and Test Proceduresfor 2001 and Subsequent Model Motor Vehicles, Mar. 22, 2012).

Determination of Working Capacity and Emissions According to a China 6Type Test Procedure (Herein and in the Claims, the “China 6 Type TestProcedure”)

Preconditioning Step. The canister system is aged by bubbling air at arate of 200 ml/min through 2 liters of EPA Tier III fuel (9 RVP, 10%ethanol) heated to 38° C. The air flow rate is controlled using a massflow controller. Under these conditions, the vapor generation rate isabout 40 g/h and the hydrocarbon concentration was approximately 50%(volume). These vapors are introduced to the canister until breakthroughof 5000 ppm is detected at the atmospheric port (if breakthrough is notdetected after 90 minutes, the gasoline is replaced). Within 2 minutes,the canister system is then purged with pressurized dry air into theatmospheric port and out of the purge (engine) port at a rate of 22.7liters/min for 300 bed volumes. This sequence is repeated for a total ofat least 35 cycles. The resulting GWC is then calculated as the averageof the last three load and purge cycles and does not include the 2 g ofbreakthrough. The test canisters is then loaded with 50:50 vol %butane-nitrogen at a rate of 40 g/h butane to a 2 g breakthroughequivalent.

Elevated Temperature Soak Step. Mimicking the expected vapor space of a70 L PATAC 358 tank (filled to 40%), a 68 L tank is filled with 25.7 L(38%) of EPA Tier III fuel (9 RVP, 10% ethanol). The canister system isthen connected to the tank and the entire system is then placed in atemperature-controlled chamber (already preheated to 38° C.) for about22 hrs. In order to avoid chamber contamination and to be able tomeasure the canister breakthrough amount during this heat build and hightemperature soak step, the canister system is vented into a “slavecanister” (2.1 L Nuchar® BAX 1500) of low restriction.

Elevated Temperature Purge. The canister system, while remaining in theheated chamber, is now purged with vacuum for 19.5 min. During thistime, the vacuum level was adjusted to maintain a flow rate of −25 L/min(incoming air) in order to achieve a theoretical purge air target of487.5 L. The total flow (including removed hydrocarbons) issimultaneously measured outside the chamber with a dry gas meter.Following this purge cycle, the system is now allowed to rest at 38° C.for 1 hr; hot soak emissions are not measured during this period, due tothe nature of this system test compared with the actual vehicle test ofthe full vehicle test protocol (no temperature gradient present withoutan actual vehicle).

20° C. Soak and 2-Day-Diurnal. The chamber is then opened to record thecanister weight and to adjust the temperature to 20° C. for the upcomingsoak period (6-36 hrs). Subsequent to this soak, the canister is againweighed and re-connected to the tank for the diurnal emission test. AKynar® bag is connected to the atmospheric port of the canister system,and the chamber is programmed to control the temperature based on the EUdiurnal temperature profile (20→35→20° C.). After 6 hrs, the bag isremoved and replaced with a new one (e.g., a single bag is typicallyinsufficient in size to capture the full 12 hrs of emissions). Theemissions in the removed Kynar® bag are measured by a flame ionizationdetector (FID). After 12 hrs, the second Kynar® bag is removed, and theemissions are also measured. The canister is weighed and reconnected tothe tank. During the cool-down portion of the diurnal cycle, no bag isattached to the canister system in order to allow for back-purge. Thesame procedure is repeated on the second day. The test is stopped afterthe heat-up portion (12 hr) of the second day. The day 2 emissions arethe total emissions from that second day as captured by the two Kynar®bags and measured by FID.

Determination of Pore Volumes and Surface Areas

Volume of pores (PV)<1.8 nm to 100 nm in size is measured by nitrogenadsorption porosimetry by the nitrogen gas adsorption method ISO15901-2:2006 using a Micromeritics ASAP 2420 (Norcross, Ga.). Because ofthe correlation of ASTM BWC with pores 1.8-5.0 nm in size, thedefinition of total mesopores herein are pores 1.8-50 nm in size(divided between small mesopores 1.8-5 nm and larger mesopores 5-50 nmin size), compared with the IUPAC definition total mesopores as pore2.0-50 nm in size. Accordingly, the micropore definition herein ispores<1.8 nm in size, as compared with the IUPAC definition of pores<2.0nm in size. “Micropores” as referred in U.S. Pat. No. 9,174,195 for thepore volume value “m” are pores with a size of less than about 100 nm.The sample preparation procedure for nitrogen adsorption testing was todegas to a pressure of less than 10 μmHg. The determination of porevolumes for pores<1.8 nm to 100 nm in size was from the desorptionbranch of the 77 K isotherm for a 0.1 g sample. The nitrogen adsorptionisotherm data was analyzed by the Kelvin and Halsey equations todetermine the distribution of pore volume with pore size of cylindricalpores according to the model of Barrett, Joyner, and Halenda (“BJH”).The non-ideality factor was 0.0000620. The density conversion factor was0.0015468. The thermal transpiration hard-sphere diameter was 3.860 Å.The molecular cross-sectional area was 0.162 nm². The condensed layerthickness (Å) related to pore diameter (D, Å) used for the calculationswas 0.4977 [ln(D)]²−0.6981 ln(D)+2.5074. Target relative pressures forthe isotherm were the following: 0.04, 0.05, 0.085, 0.125, 0.15, 0.18,0.2, 0.355, 0.5, 0.63, 0.77, 0.9, 0.95, 0.995, 0.95, 0.9, 0.8, 0.7, 0.6,0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.12, 0.1, 0.07, 0.05, 0.03,0.01. Actual points were recorded within an absolute or relativepressure tolerance of 5 mmHg or 5%, respectively, whichever was morestringent. Time between successive pressure readings duringequilibration was 10 seconds. Volumetric pore volumes in units of cc percc-pellet were obtained by multiplying the gravimetric pore volume inunits of cc/g by the particle density<100 microns in units of g/cc, asobtained by Hg porosimetry.

Macroscopic pore volume in pores 0.05-100 microns in size and particledensity is measured by mercury intrusion porosimetry method ISO15901-1:2016. The equipment used for the examples was a MicromeriticsAutopore V (Norcross, Ga.). Samples used were around 0.4 g in size andpre-treated for at least 1 hour in an oven at 105° C. The surfacetension of mercury and contact angle used for the Washburn equation were485 dynes/cm and 130°, respectively. Macropores as referred to herein,are those that have a pore size or width of from about 0.05 to 100microns. For calculating the M/m of U.S. Pat. No. 9,174,195, the totalmacropore volume ‘M’ was for pores of 0.1 to 100 microns in size.Volumetric pore volumes in units of cc per cc-pellet (cc/cc) wereobtained by multiplying the gravimetric pore volume (units of cc/g) bythe particle density<100 microns in size (units of g/cc), as obtained byHg intrusion porosimetry.

Determination of Incremental Adsorption Capacity

McBain method. The representative adsorbent component sample (“adsorbentsample”) is oven-dried for more than 3 hours at 110° C. before loadingonto a sample pan attached to a spring inside a sample tube. Then, thesample tube is installed into an apparatus as described. The adsorbentsample shall include representative amounts of any inert binders,fillers and structural components present in the nominal volume of theadsorbent component when the Apparent Density value determinationequivalently includes the mass of the inert binders, fillers, andstructural components in its mass numerator. Conversely, the adsorbentsample shall exclude these inert binders, fillers, and structuralcomponents when the Apparent Density value equivalently excludes themass of the inert binders, fillers, and structural components in itsnumerator. The universal concept is to accurately define the adsorptiveproperties for butane on a volume basis within the nominal volume.

A vacuum of less than 1 torr is applied to the sample tube, and theadsorbent sample is heated at 105° C. for 1 hour. The mass of theadsorbent sample is then determined by the extension amount of thespring using a cathetometer. After that, the sample tube is immersed ina temperature-controlled water bath at 25° C. Air was pumped out of thesample tube until the pressure inside the sample tube is 10⁻⁴ torr.n-Butane is introduced into the sample tube until equilibrium wasreached at a selected pressure. The tests are performed for two datasets of four selected equilibrium pressures each, taken about 38 torrand taken about 380 torr. The concentration of n-butane is based on theequilibrium pressure inside the sample tube. After each test at theselected equilibrium pressure, the mass of the adsorbent sample ismeasured based on the extension amount of the spring using cathetometer.The increased mass of the adsorbent sample is the amount of n-butaneadsorbed by the adsorbent sample. The mass of n-butane absorbed (ingram) per the mass of the adsorbent sample (in gram) is determined foreach test at different n-butane equilibrium pressures and plotted in agraph as a function of the concentration of n-butane (in % volume). A 5vol % n-butane concentration (in volume) at one atmosphere is providedby the equilibrium pressure inside the sample tube of 38 torr. A 50 vol% n-butane concentration at one atmosphere is provided by theequilibrium pressure inside the sample tube of 380 torr. Becauseequilibration at precisely 38 torr and 380 torr may not be readilyobtained, the mass of adsorbed n-butane per mass of the adsorbent sampleat 5 vol % n-butane concentration and at 50 vol % n-butane concentrationis interpolated from a graph using the data points collected about thetarget 38 and 380 torr pressures. Alternatively, Micromeritics (such asMicromeritics ASAP 2020) may be used for determining the incrementalbutane adsorption capacity instead of the McBain method.

Exemplary Embodiments

In an aspect, the description provides a shaped adsorbent materialcomprising an admixture of a binder and an activated adsorbent powderprepared by grinding an activated adsorbent precursor, wherein theadmixture is shaped into a form, and wherein the shaped adsorbentmaterial has an ASTM BWC of at least 13 g/dL.

In an additional aspect, the description provides a shaped adsorbentmaterial produced according to the steps comprising: providing anactivated adsorbent precursor; grinding the activated adsorbentprecursor to a powder, wherein the powder has a pBACT of at least about50 g/100 g; admixing the powder with a binder material; and shaping thepowder and binder material mixture into a form, wherein the shapedadsorbent material has an ASTM BWC of at least 13 g/dL.

In any of the aspects or embodiments of the shaped adsorbent material asdescribed herein, activated adsorbent powder precursor of the describedshaped adsorbent material has as butane activity (pBACT) of at leastabout 50 g/100 g. In any of the aspects or embodiments of the shapedadsorbent material as described herein, the activated adsorbentprecursor is an activated carbon precursor. In any of the aspects orembodiments of the shaped adsorbent material as described herein, theshaped adsorbent material comprises a ratio of pore volumes of 0.05-1micron to 0.05-100 microns that is greater than about 80%.

In any of the aspects or embodiments of the shaped adsorbent material asdescribed herein, the shaped adsorbent material comprises a ratio ofpore volumes of 0.05-0.5 micron to 0.05-100 microns that is greater thanabout 50%.

In any of the aspects or embodiments of the shaped adsorbent material asdescribed herein, the binder comprises at least one of an organicbinder, an inorganic binder or both.

In any of the aspects or embodiments of the shaped adsorbent material asdescribed herein, the organic binder is at least one of carboxymethylcellulose (CMC), a synthetic organic binder or both.

In any of the aspects or embodiments of the shaped adsorbent material asdescribed herein, the inorganic binder is a clay.

In any of the aspects or embodiments of the shaped adsorbent material asdescribed herein, the binder is CMC and is present in an amount of lessthan about 8 wt %. all values in between.

In any of the aspects or embodiments of the shaped adsorbent material asdescribed herein, the binder is bentonite clay and is present in anamount of from about 10 wt % to about 35 wt. all values in between.

In another aspect, the description provides an evaporative emissioncontrol canister system comprising at least one adsorbent volume, andincluding a shaped adsorbent material, as described herein, e.g.,comprising an admixture of a binder and an activated adsorbent powderderived by grinding an activated adsorbent precursor, wherein theadmixture is shaped into a form, and wherein the shaped adsorbentmaterial has an ASTM BWC of at least 13 g/dL.

In any of the aspects or embodiments as described herein, the canistersystem comprises at least one fuel-side adsorbent volume and at leastone vent-side adsorbent volume, wherein at least one of the at least onefuel-side adsorbent volumes or at least one vent-side adsorbent volumesor a combination thereof includes a shaped adsorbent material comprisingan admixture of a binder and an activated adsorbent powder derived bygrinding an activated adsorbent precursor, wherein the admixture isshaped into a form, and wherein the shaped adsorbent material has anASTM BWC of at least 13 g/dL.

In any of the aspects or embodiments as described herein, the shapedadsorbent material of the canister system as described herein has atleast one of: (i) a ratio of pore volumes of 0.05-1 micron to 0.05-100microns that is greater than about 80%, (ii) a ratio of pore volumes of0.05-0.5 micron to 0.05-100 microns that is greater than about 50%, or(iii) a combination thereof.

In any of the aspects or embodiments as described herein, the shapedadsorbent material as described herein has two-day diurnal breathingloss (DBL) emissions of 100 mg or less at 315 liters of purge appliedafter a 40 g/hr butane loading step as determined in a Defined Canisterby the 2012 California Bleed Emissions Test Procedure (BETP).

In any of the aspects or embodiments as described herein, the canistersystem has two-day diurnal breathing loss (DBL) emissions of less than100 mg when tested by the China 6 Type Test Procedure.

In any of the aspects or embodiments as described herein, the canistersystem comprises at least one vent-side adsorptive volume having atleast one of: (i) an incremental adsorption capacity at 25° C. of from 4grams n-butane/L to less than 35 grams n-butane/L between vaporconcentrations of 5 vol % and 50 vol % n-butane, (ii) an effective BWCof less than 3 g/dL, (iii) a g-total BWC of less than 6 grams, or (iv) acombination thereof.

In any of the aspects or embodiments as described herein, the canistersystem comprises at least one fuel-side adsorptive volume having anincremental adsorption capacity at 25° C. of greater than 35 gramsn-butane/L between vapor concentrations of 5 vol % and 50 vol %n-butane.

In any of the aspects or embodiments of the shaped adsorbent material asdescribed herein, the activated carbon precursor is derived from atleast one of wood, wood dust, wood flour, cotton linters, peat, coal,coconut, lignite, carbohydrates, petroleum pitch, petroleum coke, coaltar pitch, fruit pits, fruit stones, nut shells, nut pits, sawdust,palm, vegetables, a synthetic polymer, natural polymer, lignocellulosicmaterial, or a combination thereof.

In any of the aspects or embodiments of the shaped adsorbent material asdescribed herein, the form is selected from a pellet, granule, sphere,honeycomb, monolith, cylinder, particulate, hollow-cylinder, star,twisted spiral, asterisk, configured ribbon, or a combination thereof.

In any of the aspects or embodiments described herein, the evaporativeemission control canister system has two-day diurnal breathing loss(DBL) emissions of 20 mg or less with no more than 315 liters of purgeapplied after a 40 g/hr butane loading step as determined by the 2012California Bleed Emissions Test Procedure (BETP).

In any of the aspects or embodiments described herein, the evaporativeemission control canister system has two-day diurnal breathing loss(DBL) emissions of 20 mg or less with no more than 150 BV of purgeapplied after a 40 g/hr butane loading step as determined by the 2012California Bleed Emissions Test Procedure (BETP).

The contents of all references, patents, pending patent applications andpublished patents, cited throughout this application are herebyexpressly incorporated by reference.

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, many equivalents to the specificembodiments of the invention described herein. Such equivalents areintended to be encompassed by the following claims. It is understoodthat the detailed examples and embodiments described herein are given byway of example for illustrative purposes only, and are in no wayconsidered to be limiting to the invention. Various modifications orchanges in light thereof will be suggested to persons skilled in the artand are included within the spirit and purview of this application andare considered within the scope of the appended claims. For example, therelative quantities of the ingredients may be varied to optimize thedesired effects, additional ingredients may be added, and/or similaringredients may be substituted for one or more of the ingredientsdescribed. Additional advantageous features and functionalitiesassociated with the systems, methods, and processes of the presentinvention will be apparent from the appended claims. Moreover, thoseskilled in the art will recognize, or be able to ascertain using no morethan routine experimentation, many equivalents to the specificembodiments of the invention described herein. Such equivalents areintended to be encompassed by the following claims.

The invention claimed is:
 1. An evaporative emission control canistersystem comprising: at least one adsorbent volume, and including a shapedadsorbent material comprising an admixture of a binder and an activatedadsorbent powder having a butane activity (pBACT) of at least about 50g/100 g, derived by grinding an activated adsorbent precursor, whereinthe admixture is shaped into a form, wherein the shaped adsorbentmaterial has an ASTM BWC of at least 13 g/dL, and at least one of: (i) aratio of pore volumes of 0.05-1 micron to 0.05-100 microns that isgreater than about 80%, (ii) a ratio of pore volumes of 0.05-0.5 micronto 0.05-100 microns that is greater than about 50%, or (iii) acombination thereof.
 2. The evaporative emission control canister systemof claim 1, wherein the canister system comprises at least one fuel-sideadsorbent volume and at least one vent-side adsorbent volume, wherein atleast one of the at least one fuel-side adsorbent volumes or at leastone vent-side adsorbent volumes or a combination thereof includes theshaped adsorbent material of claim
 1. 3. The evaporative emissioncontrol canister system of claim 1, wherein the shaped adsorbentmaterial has two-day diurnal breathing loss (DBL) emissions of 100 mg orless at 315 liters of purge applied after a 40 g/hr butane loading stepas determined in a Defined Canister by the 2012 California BleedEmissions Test Procedure (BETP).
 4. The evaporative emission controlcanister system of claim 1, wherein the system has two-day diurnalbreathing loss (DBL) emissions of less than 100 mg when tested by China6 Type Test Procedure.
 5. The evaporative emission control canistersystem of claim 1, wherein the activated adsorbent precursor is anactivated carbon precursor.
 6. The evaporative emission control canistersystem of claim 1, wherein the binder comprises at least one of anorganic binder, an inorganic binder or both.
 7. The evaporative emissioncontrol canister system of claim 6, wherein the organic binder is atleast one of carboxymethyl cellulose (CMC), a synthetic organic binderor both.
 8. The evaporative emission control canister system of claim 6,wherein the inorganic binder is a clay.
 9. The evaporative emissioncontrol canister system of claim 5, wherein the activated carbonprecursor is derived from at least one of wood, wood dust, wood flour,cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleumpitch, petroleum coke, coal tar pitch, fruit pits, fruit stones, nutshells, nut pits, sawdust, palm, vegetables, a synthetic polymer,natural polymer, lignocellulosic material, or a combination thereof. 10.The evaporative emission control canister system of claim 1, wherein theform is selected from a pellet, granule, sphere, honeycomb, monolith,cylinder, particulate, hollow-cylinder, star, twisted spiral, asterisk,configured ribbon, or a combination thereof.
 11. The evaporativeemission control canister system of claim 1, wherein the canister systemcomprises at least one vent-side adsorptive volume having at least oneof: (i) an incremental adsorption capacity at 25° C. of from 4 gramsn-butane/L to less than 35 grams n-butane/L between vapor concentrationsof 5 vol % and 50 vol % n-butane, (ii) an effective BWC of less than 3g/dL, (iii) a g-total BWC of less than 6 grams, or (iv) a combinationthereof.
 12. The evaporative emission control canister system of claim1, wherein the canister system comprises at least one fuel-sideadsorptive volume having an incremental adsorption capacity at 25° C. ofgreater than 35 grams n-butane/L between vapor concentrations of 5 vol %and 50 vol % n-butane.
 13. The evaporative emission control canistersystem of claim 1, wherein the system has two-day diurnal breathing loss(DBL) emissions of 20 mg or less with no more than 315 liters of purgeapplied after a 40 g/hr butane loading step as determined by the 2012California Bleed Emissions Test Procedure (BETP).
 14. The evaporativeemission control canister system of claim 1, wherein the system hastwo-day diurnal breathing loss (DBL) emissions of 20 mg or less with nomore than 150 BV of purge applied after a 40 g/hr butane loading step asdetermined by the 2012 California Bleed Emissions Test Procedure (BETP).